Chemical liquid, pattern forming method, and kit

ABSTRACT

An object of the present invention is to provide a chemical liquid which makes it possible to form a thinner resist film having a uniform thickness on a substrate by using a small amount of resist composition and demonstrates excellent defect inhibition performance. Another object of the present invention is to provide a pattern forming method. A chemical liquid of the present invention contains a mixture of two or more kinds of organic solvents, in which the organic solvents are selected from the group consisting of compounds represented by Formulae (1) to (7), compounds represented by Formulae (9) to (11), a 3- to 5-membered cyclic ketone compound that may have a substituent, a cyclic ketone compound with 6 or more members that may have a substituent, a lactone compound, and a lactam compound, the chemical liquid contains or does not contain an ether-based compound other than the compounds represented by Formula (1), Formula (5), Formula (7), and Formulae (9) to (11), and in a case where the chemical liquid contains the ether-based compound, a content of the ether-based compound in the chemical liquid is less than 10 mass ppm with respect to a total mass of the chemical liquid.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of PCT International Application No.PCT/JP2017/040904 filed on Nov. 14, 2017, which claims priority under 35U.S.C. § 119(a) to Japanese Patent Application No. 2016-225410 filed onNov. 18, 2016, Japanese Patent Application No. 2017-030903 filed on Feb.22, 2017 and Japanese Patent Application No. 2017-217992 filed on Nov.13, 2017. Each of the above applications is hereby expresslyincorporated by reference, in its entirety, into the presentapplication.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a chemical liquid, a pattern formingmethod, and a kit.

2. Description of the Related Art

During the photolithography process in a semiconductor devicemanufacturing process, a substrate such as a semiconductor wafer(hereinafter, referred to as “wafer” as well) is coated with an actinicray-sensitive or radiation-sensitive resin composition (hereinafter,referred to as “resist composition” as well) so as to form an actinicray-sensitive or radiation-sensitive film (hereinafter, referred to as“resist film” as well). Furthermore, steps of exposing the formed resistfilm, developing the exposed resist film so as to form a predeterminedpattern, and the like are sequentially performed, and in this way, aresist pattern is formed on the wafer.

In recent years, as semiconductor devices have been further scaled down,thinning of resist films have been required. Furthermore, there has beena demand for a technique of forming a uniform resist film by using asmall amount of resist composition. As such a technique, a method isknown in which a substrate is coated with a chemical liquid calledprewet agent before the substrate is coated with a resist composition.In JP2007-324393A, as a prewet agent, a solution is described which isobtained by mixing together a solvent having low volatility and asolvent having low surface tension at a predetermined ratio.

SUMMARY OF THE INVENTION

The inventors of the present invention coated a substrate with theprewet agent described in JP2007-324393A and then with a resistcomposition. As a result, the inventors have found that depending on thecombination of organic solvents, it is difficult to form a thinnerresist film having a uniform thickness on the substrate by using a smallamount of the resist composition, or defect inhibition performancebecomes insufficient. Furthermore, the inventors have found that in acase where the prewet agent contains one kind of organic solvent,sometimes it is difficult to form a resist film due to the variation inthe components constituting the resist film and/or stable defectinhibition performance cannot be obtained.

An object of the present invention is to provide a chemical liquid whichmakes it possible to form a thinner resist film having a uniformthickness on a substrate by using a small amount of resist composition(hereinafter, the above properties will be described as having excellent“resist saving properties” as well) and demonstrates excellent defectinhibition performance. Another object of the present invention is toprovide a chemical liquid storage body and a pattern forming method.

In the present specification, the resist saving properties and thedefect inhibition performance mean the resist saving properties and thedefect inhibition performance measured by the method described inExamples.

In order to achieve the aforementioned objects, the inventors of thepresent invention carried out an intensive examination. As a result, theinventors have found that the objects can be achieved by the followingconstitution.

[1] A chemical liquid comprising a mixture of two or more kinds oforganic solvents, in which the organic solvents are selected from thegroup consisting of compounds represented by Formulae (1) to (7),compounds represented by Formulae (9) to (11), a 3- to 5-membered cyclicketone compound that may have a substituent, a cyclic ketone compoundwith 6 or more members that may have a substituent, a lactone compound,and a lactam compound, the chemical liquid contains or does not containan ether-based compound other than the compounds represented by Formula(1), Formula (5), Formula (7), and Formulae (9) to (11), in a case wherethe chemical liquid contains the ether-based compound, a content of theether-based compound in the chemical liquid is less than 10 mass ppmwith respect to a total mass of the chemical liquid, and the chemicalliquid does not include a chemical liquid in which the mixture is formedof a lactone compound and the compound represented by Formula (5), achemical liquid in which the mixture is formed of the cyclic ketonecompound with 6 or more members that may have a substituent and thecompound represented by Formula (1), a chemical liquid in which themixture is formed of a lactone compound, the compound represented byFormula (1), and the compound represented by Formula (5), and a chemicalliquid in which the mixture is formed of the compound represented byFormula (1) and the compound represented by Formula (3).

[2] A chemical liquid comprising a mixture of two or more kinds oforganic solvents, in which the mixture contains γ-butyrolactone and atleast one kind of organic solvent selected from the group consisting ofbutyl acetate, ethyl lactate, 2-hydroxymethyl isobutyrate,cyclopentanone dimethyl acetal, cyclopentanone, anisole, phenetole,ethylene glycol monomethyl ether acetate, 3-methoxymethyl propionate,and 3-ethoxyethyl propionate, contains dimethyl sulfoxide and at leastone kind of organic solvent selected from the group consisting ofpropylene glycol monomethyl ether acetate, butyl acetate, ethyl lactate,2-hydroxymethyl isobutyrate, propylene glycol monomethyl ether,cyclopentanone dimethyl acetal, cyclopentanone, cyclohexanone, anisole,phenetole, ethylene glycol monomethyl ether acetate, 3-methoxymethylpropionate, and 3-ethoxyethyl propionate, contains ethylene carbonateand at least one kind of organic solvent selected from the groupconsisting of propylene glycol monomethyl ether acetate, butyl acetate,ethyl lactate, 2-hydroxymethyl isobutyrate, propylene glycol monomethylether, cyclopentanone dimethyl acetal, cyclopentanone, cyclohexanone,anisole, phenetole, ethylene glycol monomethyl ether acetate,3-methoxymethyl propionate, and 3-ethoxyethyl propionate, containspropylene carbonate and at least one kind of organic solvent selectedfrom the group consisting of propylene glycol monomethyl ether acetate,butyl acetate, ethyl lactate, 2-hydroxymethyl isobutyrate, propyleneglycol monomethyl ether, cyclopentanone dimethyl acetal, cyclopentanone,cyclohexanone, anisole, phenetole, ethylene glycol monomethyl etheracetate, 3-methoxymethyl propionate, and 3-ethoxyethyl propionate,contains 1-methyl-2-pyrrolidone and at least one kind of organic solventselected from the group consisting of propylene glycol monomethyl etheracetate, butyl acetate, ethyl lactate, 2-hydroxymethyl isobutyrate,propylene glycol monomethyl ether, cyclopentanone dimethyl acetal,cyclopentanone, cyclohexanone, anisole, phenetole, ethylene glycolmonomethyl ether acetate, 3-methoxymethyl propionate, and 3-ethoxyethylpropionate, contains propylene glycol monomethyl ether acetate and atleast one kind of organic solvent selected from the group consisting ofbutyl acetate, cyclopentanone dimethyl acetal, cyclopentanone, anisole,phenetole, ethylene glycol monomethyl ether acetate, 3-methoxymethylpropionate, and 3-ethoxyethyl propionate, contains cyclohexanone and atleast one kind of organic solvent selected from the group consisting ofbutyl acetate, ethyl lactate, 2-hydroxymethyl isobutyrate, propyleneglycol monomethyl ether, cyclopentanone dimethyl acetal, cyclopentanone,anisole, phenetole, ethylene glycol monomethyl ether acetate,3-methoxymethyl propionate, and 3-ethoxyethyl propionate, contains ethyllactate and at least one kind of organic solvent selected from the groupconsisting of butyl acetate, propylene glycol monomethyl ether,cyclopentanone dimethyl acetal, cyclopentanone, anisole, phenetole,ethylene glycol monomethyl ether acetate, 3-methoxymethyl propionate,and 3-ethoxyethyl propionate, contains 2-hydroxymethyl isobutyrate andat least one kind of organic solvent selected from the group consistingof butyl acetate, propylene glycol monomethyl ether, cyclopentanonedimethyl acetal, cyclopentanone, anisole, phenetole, ethylene glycolmonomethyl ether acetate, 3-methoxymethyl propionate, and 3-ethoxyethylpropionate, or contains cyclopentanone dimethyl acetal and at least onekind of organic solvent selected from the group consisting of butylacetate, propylene glycol monomethyl ether, cyclopentanone, anisole,phenetole, ethylene glycol monomethyl ether acetate, 3-methoxymethylpropionate, and 3-ethoxyethyl propionate.

[3] The chemical liquid described in [1] or [2], comprising a mixture oftwo or more kinds of the organic solvents.

[4] The chemical liquid described in any one of [1] to [3], in which avapor pressure of the mixture is 160 to 1,000 Pa at 25° C.

[5] The chemical liquid described in any one of [1] to [4], in which themixture contains a first organic solvent which has a vapor pressure of160 to 1,000 Pa at 25° C. and a second organic solvent which has a vaporpressure higher than 1,000 Pa at 25° C. or contains two or more kinds ofthe first organic solvents.

[6] The chemical liquid described in any one of [1] to [5], in which themixture contains a third organic solvent which has a vapor pressurelower than 160 Pa at 25° C.

[7] The chemical liquid described in any one of [1] to [6], in which asurface tension of the mixture is equal to or higher than 28 mN/m at 25°C.

[8] The chemical liquid described in any one of [1] to [7], in which themixture contains an organic solvent having a Hansen solubility parameterhigher than 9.5 (MPa)^(0.5) in terms of a hydrogen bond element orhaving a Hansen solubility parameter higher than 15.5 (MPa)^(0.5) interms of a dispersion element.

[9] The chemical liquid described in any one of [1] to [8] that is usedfor pre-wetting.

[10] A pattern forming method comprising a pre-wetting step of coating asubstrate with the chemical liquid described in any one of [1] to [9] soas to obtain a pre-wetted substrate, a resist film forming step offorming a resist film on the pre-wetted substrate by using an actinicray-sensitive or radiation-sensitive resin composition, an exposure stepof exposing the resist film, and a development step of developing theexposed resist film by using a developer, in which the actinicray-sensitive or radiation-sensitive resin composition contains a resinincluding at least one kind of repeating unit selected from the groupconsisting of a repeating unit represented by Formula (a), a repeatingunit represented by Formula (b), a repeating unit represented by Formula(c), a repeating unit represented by Formula (d), and a repeating unitrepresented by Formula (e) that will be described later.

[11] The pattern forming method described in [10], in which the chemicalliquid with which the substrate is coated in the pre-wetting stepsatisfies the following conditions 1 and 2 that will be described laterat 25° C.

[12] A kit comprising the chemical liquid described in any one of [1] to[9] and an actinic ray-sensitive or radiation-sensitive resincomposition which contains a resin including at least one kind ofrepeating unit selected from the group consisting of a repeating unitrepresented by Formula (a), a repeating unit represented by Formula (b),a repeating unit represented by Formula (c), a repeating unitrepresented by Formula (d), and a repeating unit represented by Formula(e) that will be described later.

[13] A kit comprising the chemical liquid described in any one of [1] to[9] and an actinic ray-sensitive or radiation-sensitive resincomposition, in which the actinic ray-sensitive or radiation-sensitiveresin composition contains a resin which has a repeating unit having aphenolic hydroxyl group and has a group generating a polar group bybeing decomposed by the action of an acid.

[14] A kit comprising the chemical liquid described in any one of [1] to[9] and an actinic ray-sensitive or radiation-sensitive resincomposition, in which the actinic ray-sensitive or radiation-sensitiveresin composition contains a hydrophobic resin and a resin which has agroup generating a polar group by being decomposed by the action of anacid.

[15] A kit comprising the chemical liquid described in any one of [1] to[9] and an actinic ray-sensitive or radiation-sensitive resincomposition containing a resin, in which the kit satisfies Condition 1and Condition 2 that will be described later.

According to the present invention, it is possible to provide a chemicalliquid which has excellent resist saving properties and excellent defectinhibition performance (hereinafter, described as “having the effects ofthe present invention” as well). Furthermore, according to the presentinvention, it is possible to provide a pattern forming method and a kit.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Hereinafter, the present invention will be specifically described.

The following constituents will be described based on typicalembodiments of the present invention in some cases, but the presentinvention is not limited to the embodiments.

In the present specification, a range of numerical values describedusing “to” means a range including the numerical values listed beforeand after “to” as a lower limit and an upper limit respectively.

In the present invention, “preparation” means not only the preparationof a specific material by means of synthesis or mixing but also thepreparation of a predetermined substance by means of purchase and thelike.

In the present specification, “ppm” means “parts-per-million (10⁻⁶)”,“ppb” means “parts-per-billion (10⁻⁹)”, “ppt” means “parts-per-trillion(10⁻¹²)”, and “ppq” means “parts-per-quadrillion (10⁻¹⁵)”.

In the present invention, 1 Å (angstrom) equals 0.1 nm.

In the present invention, regarding the description of a group (atomicgroup), in a case where whether the group is substituted orunsubstituted is not described, as long as the effects of the presentinvention are not impaired, the group includes a group which does nothave a substituent and a group which has a substituent. For example,“alkyl group” includes not only an alkyl group which does not have asubstituent (unsubstituted alkyl group) but also an alkyl group whichhas a substituent (substituted alkyl group). The same is true for eachcompound.

Furthermore, in the present invention, “radiation” means, for example,far ultraviolet rays, extreme ultraviolet (EUV), X-rays, electron beams,and the like. In addition, in the present invention, light means actinicrays or radiation. In the present invention, unless otherwise specified,“exposure” includes not only exposure, far ultraviolet rays, X-rays, andEUV, and the like, but also lithography by particle beams such asElectron beams or ion beams.

[Chemical Liquid]

The chemical liquid according to a first embodiment of the presentinvention (hereinafter, this chemical liquid will be simply referred toas “chemical liquid” in some cases in the present specification) is achemical liquid containing a mixture of two or more kinds of organicsolvents, in which the organic solvents are selected from predeterminedcompounds, the chemical liquid contains or does not contain apredetermined ether-based compound, and in a case where the chemicalliquid contains the predetermined ether-based compound, a content of thepredetermined ether-based compound in the chemical liquid with respectto a total mass of the chemical liquid is less than 10 mass ppm. Here,the chemical liquid does not include a chemical liquid in which themixture is formed of a lactone compound and a compound represented byFormula (5), a chemical liquid in which the mixture is formed of acyclic ketone compound with 6 or more members that may have asubstituent and a compound represented by Formula (1), a chemical liquidin which the mixture is formed of a lactone compound, the compoundrepresented by Formula (1), and the compound represented by Formula (5),and a chemical liquid in which the mixture is formed of the compoundrepresented by Formula (1) and a compound represented by Formula (3).

[Ether-Based Compound]

The chemical liquid according to the embodiment contains or does notcontain an ether-based compound other than compounds represented byFormula (1), Formula (5), Formula (7), and Formulae (9) to (11)(hereinafter, these compounds will be referred to as “specificcompounds” as well). In a case where the chemical liquid contains theether-based compound, the content of the ether-based compound in thechemical liquid with respect to the total mass of the chemical liquid isless than 10 mass ppm.

In the present specification, the ether-based compound and the organicsolvents which will be described later mean different components.

In a case where the chemical liquid according to the embodiment containsthe ether-based compound, the content of the ether-based compound in thechemical liquid with respect to the total mass of the chemical liquid isless than 10 mass ppm, and preferably equal to or smaller than 5 massppm.

One kind of the ether-based compound may be used singly, or two or morekinds of the ether-based compounds may be used in combination. In a casewhere two or more kinds of the ether-based compounds are used incombination, the total content thereof is preferably within the aboverange.

It is preferable that the chemical liquid according to the embodimentdoes not contain the ether-based compound, because then the chemicalliquid has further improved defect inhibition performance. In thepresent specification, “substantially does not contain the ether-basedcompound” means that the ether-based compound is not detected in a casewhere the chemical liquid is measured using the method of Examples byusing gas chromatography mass spectrometry which will be describedlater.

In a case where the chemical liquid does not contain the ether-basedcompound or in a case where the chemical liquid contains the ether-basedcompound but the content thereof is within the above range, the effectsof the present invention are obtained. Although the mechanism thatbrings about the effects is not unclear, particularly in a case wherethe surface tension of the mixture of organic solvents, which will bedescribed later, is equal to or lower than 40 mN/m, the effects becomeapparent.

As the ether-based compound, known compounds can be used withoutparticular limitation as long as the ether-based compound is notincluded in the specific compounds. Examples of the ether-based compoundinclude hydrocarbon-based compounds such as glycol ether. Examples ofthe hydrocarbon-based compounds include dialkylene glycol alkyl ether,dialkylene glycol dialkyl ether, alkylene glycol dialkyl ether, alkyleneglycol alkyl ether, and the like. More specifically, examples of theseinclude diethylene glycol methyl ethyl ether, ethylene glycol methylether, diethylene glycol methyl ether, diethylene glycol ethyl ether,diethylene glycol butyl ether, diethylene glycol dimethyl ether,diethylene glycol diethyl ether, and the like.

As the ether-based compound, for example, a compound represented byFormula (8) can be used.

In Formula (8), n represents an integer equal to or greater than 1. Theupper limit of n is not particularly limited, but is preferably equal toor smaller than 3.

The molecular weight of the ether-based compound is not particularlylimited. Generally, the molecular weight of the ether-based compound ispreferably less than 1,000, more preferably less than 500, and even morepreferably less than 200.

It is preferable that the ether-based compound (particularly, thehydrocarbon-based compound) contain none of fluorine (F) and silicone(Si). In a case where the ether-based compound contains none of these,it is possible to prevent the phenomenon in which the ether-basedcompound molecules are aggregated due to fluorine and/or silicon and/orthe phenomenon in which residues remain on a wafer due to theinteraction with components (for example, a resin which will bedescribed later and the like) in the wafer and/or a resist solution.

[Mixture of Two or More Kinds of Organic Solvents]

The chemical liquid contains a mixture of two or more kinds of organicsolvents. In a case where the chemical liquid contains the mixture oftwo or more kinds of organic solvents, unlike a chemical liquidcontaining only one kind of organic solvent, the chemical liquid can beadjusted according to the components constituting a resist film.Furthermore, regardless of the variation of the components constitutinga resist film, a stabilized resist film can be formed, or defectinhibition performance can be obtained.

The content of the mixture in the chemical liquid is not particularlylimited, but is preferably 99.9% to 100% by mass with respect to thetotal mass of the chemical liquid in general.

It is preferable that the organic solvents stay as liquids in anenvironment with −5 kPa (gauge pressure) and 80° C.

<Organic Solvents>

The organic solvents are selected from the group consisting of compoundsrepresented by Formulae (1) to (7), compound represented by Formulae (9)to (11), a 3- to 5-membered cyclic ketone compound that may have asubstituent, a cyclic ketone compound with 6 or more members that mayhave a substituent, a lactone compound, and a lactam compound.

Compound Represented by Formula (1)

In Formula (1), R₁₁ and R₁₂ each independently represent an alkyl group,R₁₃ represents a hydrogen atom or an alkyl group, and L₁ represents asingle bond or an alkylene group.

The alkyl group represented by R₁₁ and R₁₂ is not particularly limited,and may be any of a linear, branched, or cyclic alkyl group. The numberof carbon atoms in the alkyl group is not particularly limited, but ispreferably 1 to 8 in general and more preferably 1 to 6.

The number of carbon atoms in the alkylene group represented by L₁ isnot particularly limited, but is preferably 1 to 8 in general and morepreferably 1 to 6.

The compound represented by Formula (1) is not particularly limited, andexamples thereof include propylene glycol monomethyl ether acetate andthe like.

The content of the compound represented by Formula (1) in the mixture isnot particularly limited. However, the content of the compound withrespect to the total mass of the mixture is preferably 20% to 80% bymass in general.

Compound Represented by Formula (2)

In Formula (2), R₂₁ and R₂₂ each independently represent a hydrogen atomor an alkyl group, and L₂ represents a single bond or an alkylene group.The alkyl group represented by R₂₁ and R₂₂ is not particularly limited,and is as described above as the alkyl group represented by R₁₁ inFormula (1).

The alkylene group represented by L₂ is as described above as thealkylene group represented by L₁.

The compound represented by Formula (2) is not particularly limited, andexamples thereof include butyl acetate, isoamyl acetate, ethyl acetate,propyl butyrate, butyl butyrate, and the like. Among these, butylacetate is preferable.

The content of the compound represented by Formula (2) in the mixture isnot particularly limited. However, the content of the compound withrespect to the total mass of the mixture is preferably 45% to 65% bymass in general.

Compound Represented by Formula (3)

In Formula (3), R₃₁ and R₃₂ each independently represent a hydrogen atomor an alkyl group. At least one of a plurality of R₃₂'s represents analkyl group. L₃ represents a single bond or an alkylene group.

The alkyl group represented by R₃₁ and R₃₂ is not particularly limited,and is as described above as the alkyl group represented by R₁₁ inFormula (1).

The alkylene group represented by L₃ is as described above as thealkylene group represented by L₁.

The compound represented by Formula (3) is not particularly limited, andexamples thereof include methyl lactate, ethyl lactate, propyl lactate,2-hydroxymethyl isobutyrate, 2-hydroxyethyl isobutyrate, and the like.Among these, ethyl lactate or 2-hydroxymethyl isobutyrate is preferable.

The content of the compound represented by Formula (3) in the mixture isnot particularly limited. However, the content of the compound withrespect to the total mass of the mixture is preferably 10% to 100% bymass in general, and more preferably 20% to 95% by mass. The state wherethe content of the compound represented by Formula (3) in the mixture is100% by mass means that each of two or more kinds of the organicsolvents is represented by Formula (3). For example, in the mixture, thecontent of ethyl lactate is 50% by mass and the content of2-hydroxymethyl isobutyrate is 50% by mass.

Compound Represented by Formula (4)

In Formula (4), R₄₁ and R₄₂ each independently represent an alkyl group.The alkyl group represented by R₄₁ and R₄₂ is not particularly limited,and is as described above as the alkyl group represented by R₁₁ inFormula (1).

The compound represented by Formula (4) is not particularly limited, andexamples thereof include dimethyl sulfoxide, dibutyl sulfoxide, and thelike. Among these, dimethyl sulfoxide is preferable.

The content of the compound represented by Formula (4) in the mixture isnot particularly limited. However, the content of the compound withrespect to the total mass of the mixture is preferably 5% to 50% by massin general, and more preferably 5% to 30% by mass.

Compound Represented by Formula (5)

In Formula (5), R₅₁ and R₅₂ each independently represent an alkyl group,and L₅ represents a single bond or an alkylene group. The alkyl grouprepresented by R₅₁ and R₅₂ is not particularly limited, and is asdescribed above as the alkyl group represented by R₁₁ in Formula (1).

The alkylene group represented by L₅ is as described above as thealkylene group represented by L₁.

The compound represented by Formula (5) is not particularly limited, andexamples thereof include propylene glycol monomethyl ether and the like.

The content of the compound represented by Formula (5) in the mixture isnot particularly limited. However, the content of the compound withrespect to the total mass of the mixture is preferably 20% to 50% bymass in general.

Compound Represented by Formula (6)

In Formula (6), R₆₁ and R₆₂ each independently represent an alkyl group.R₆₁ and R₆₂ may form a ring by being bonded to each other.

The alkyl group represented by R₆₁ and R₆₂ Is not particularly limited,and is as described above as the alkyl group represented by R₁₁ inFormula (1).

The compound represented by Formula (6) is not particularly limited, andexamples thereof include ethylene carbonate, propylene carbonate,1,2-butylene carbonate, diethyl carbonate, dimethyl carbonate, ethylmethyl carbonate, vinylene carbonate, and the like. Among these,ethylene carbonate or propylene carbonate is preferable.

The content of the compound represented by Formula (6) in the mixture isnot particularly limited. However, the content of the compound withrespect to the total mass of the mixture is preferably 5% to 50% by massin general.

Compound Represented by Formula (7)

In Formula (7), R₇₁, R₇₂, R₇₃, and R₇₄ each independently represent analkyl group. R₇₁ and R₇₂ may form a ring by being bonded to each other.

The alkyl group represented by R₇₁ to R₇₄ is not particularly limited,and is as described above as the alkyl group represented by R₁₁ inFormula (1).

The compound represented by Formula (7) is not particularly limited, andexamples thereof include1,1-dimethoxycyclopentane(cyclopentanonedimethylacetal), cyclopentanonedimethyl acetal, 1,1-dimethoxycyclohexane, 2,2-dibutoxypropane,2,2-dimethoxypropane, and the like. Among these, cyclopentanone dimethylacetal is preferable.

The content of the compound represented by Formula (7) in the mixture isnot particularly limited. However, the content of the compound withrespect to the total mass of the mixture is preferably 20% to 95% bymass in general.

Compound Represented by Formula (9)

In Formula (9), R₉₁ and R₉₂ each independently represent an alkyl group.R₉₁ and R₉₂ may be the same as or different from each other.

The alkyl group represented by R₉₁ and R₉₂ is not particularly limited,and is as described above as the alkyl group represented by R₁₁ inFormula (1).

The compound represented by Formula (9) is not particularly limited, andexamples thereof include 3-methoxymethyl propionate (MMP), 3-ethoxyethylpropionate, and the like.

The content of the compound represented by Formula (9) in the mixture isnot particularly limited. However, the content of the compound withrespect to the total mass of the mixture is preferably 30% to 97% bymass in general.

Compound Represented by Formula (10)

In Formula (10), R₁₀₁ represents an alkyl group. The alkyl grouprepresented by R₁₀₁ is not particularly limited, and is as describedabove as the alkyl group represented by R₁₁ in Formula (1).

L₁₀ represents a single bond or an alkylene group. The alkylene grouprepresented by L₁₀ is as described above as the alkylene grouprepresented by L₁.

The compound represented by Formula (10) is not particularly limited,and examples thereof include ethylene glycol monomethyl ether acetateand the like.

The content of the compound represented by Formula (10) in the mixtureis not particularly limited. However, the content of the compound withrespect to the total mass of the mixture is preferably 50% to 90% bymass in general.

Compound Represented by Formula (11)

In Formula (11), R₁₁₁ represents an alkyl group. The alkyl grouprepresented by R₁₁₁ is not particularly limited, and is as describedabove as the alkyl group represented by R₁₁ in Formula (1).

L₁₁ represents a single bond or an alkylene group. The alkylene grouprepresented by L₁₁ is as described above as the alkylene grouprepresented by L₁.

The compound represented by Formula (11) is not particularly limited,and examples thereof include anisole, phenetole, and the like.

The content of the compound represented by Formula (11) in the mixtureis not particularly limited. However, the content of the compound withrespect to the total mass of the mixture is preferably 1.0% to 85.0% bymass in general.

3- to 5-Membered Cyclic Ketone Compound that May have a Substituent

The substituent is not particularly limited, and examples thereofinclude a linear, branched, or cyclic alkyl group, a halogen atom, ahydroxyl group, an amino group, a combination of these, and the like.

The number of members of the ring is preferably 4 or 5, and morepreferably 5.

The 3- to 5-membered cyclic ketone compound that may have a substituentis not particularly limited, and examples thereof includecyclopentanone, 2,2,4-trimethyl cyclopentanone, cyclobutanone, and thelike. Among these, cyclopentanone is preferable.

The content of the 3- to 5-membered cyclic ketone compound that may havea substituent in the mixture is not particularly limited. However, thecontent of the compound with respect to the total mass of the mixture ispreferably 20% to 60% by mass in general.

Cyclic Ketone Compound with 6 or More Members that May have aSubstituent

The substituent is not particularly limited, and examples thereofinclude a linear, branched, or cyclic alkyl group, a halogen atom, ahydroxyl group, an amino group, a combination of these, and the like.

The upper limit of the number of members of the ring is not particularlylimited, but is preferably equal to or smaller than 12, more preferablyequal to or smaller than 10, and even more preferably equal to orsmaller than 8.

The cyclic ketone compound with 6 or more members that may have asubstituent is not particularly limited, and examples thereof includecyclohexanone, 4-tert-butyl cyclohexanone, 2-chlorocyclohexanone,dimethyl cyclohexanone, 2-methoxycyclohexanone, cycloheptanone,cyclooctanone, and the like. Among these, cyclohexanone is preferable.

The content of the cyclic ketone compound with 6 or more members thatmay have a substituent in the mixture is not particularly limited.However, the content of the compound with respect to the total mass ofthe mixture is preferably 65% to 95% by mass in general.

Lactone Compound

The lactone compound is not particularly limited, and examples thereofinclude β-propiolactone, β-butyrolactone, β-valerolactone,γ-butyrolactone, γ-valerolactone, γ-caprylolactone, δ-valerolactone,β-methyl-δ-valerolactone, δ-stearolactone, ε-caprolactone, γ-octanoiclactone, 2-methyl-ε-caprolactone, 4-methyl-ε-caprolactone,ε-caprylolactone, ε-palmitolactone, α-hydroxy-γ-butyrolactone,α-methyl-γ-butyrolactone, and the like. Among these, γ-butyrolactone ispreferable.

The content of the lactone compound in the mixture is not particularlylimited. However, the content of the compound with respect to the totalmass of the mixture is preferably 5% to 50% by mass and more preferably5% to 35% by mass in general.

Lactam Compound

The lactam compound is not particularly limited, and examples thereofinclude 2-pyrrolidone, 1-methyl-2-pyrrolidone, ε-caprolactam, and thelike. Among these, 1-methyl-2-pyrrolidone is preferable.

The content of the lactam compound in the mixture is not particularlylimited. However, the content of the compound with respect to the totalmass of the mixture is preferably 5% to 50% by mass in general.

The chemical liquid contains a mixture of two or more kinds of theorganic solvents.

The mixture preferably contains at least one kind of organic solventselected from the group consisting of Formula (4), Formula (6), Formula(7), and the 3- to 5-membered cyclic ketone compound that may have asubstituent, and more preferably contains at least one kind of organicsolvent selected from the group consisting of Formula (4), Formula (6),and Formula (7). The chemical liquid containing the mixture containingthe organic solvents has further improved effects of the presentinvention.

Furthermore, the mixture preferably contains the compound represented byFormula (9) and at least one kind of compound selected from the groupconsisting of the compound represented by Formula (4) and the compoundrepresented by Formula (6), and is more preferably formed of thecompound represented by Formula (9) and the compound represented byFormula (4) or the compound represented by Formula (6).

In addition, the mixture preferably contains the compound represented byFormula (10) and at least one kind of compound selected from the groupconsisting of the compound represented by Formula (1), the compoundrepresented by Formula (3), the compound represented by Formula (4), thecompound represented by Formula (5), the compound represented by Formula(6), the compound represented by Formula (7), and a lactone compound,and is more preferably formed of the compound represented by Formula(10) and at least one kind of compound selected from the groupconsisting of the compound represented by Formula (1), the compoundrepresented by Formula (3), the compound represented by Formula (4), thecompound represented by Formula (5), the compound represented by Formula(6), the compound represented by Formula (7), and a lactone compound.

Moreover, the mixture preferably contains the compound represented byFormula (9) and at least one kind of compound selected from the groupconsisting of the compound represented by Formula (1), the compoundrepresented by Formula (3), the compound represented by Formula (4), thecompound represented by Formula (5), the compound represented by Formula(6), the compound represented by Formula (7), and a lactone compound,and is more preferably formed of the compound represented by Formula (9)and at least one kind of compound selected from the group consisting ofthe compound represented by Formula (1), the compound represented byFormula (3), the compound represented by Formula (4), the compoundrepresented by Formula (5), the compound represented by Formula (6), thecompound represented by Formula (7), and a lactone compound.

Particularly, in view of obtaining a chemical liquid having furtherimproved effects of the present invention, the mixture is even morepreferably formed of the compound represented by Formula (1) and thecompound represented by Formula (4), formed of the compound representedby Formula (4) and the compound represented by Formula (9), formed ofthe compound represented by Formula (1) and the compound represented byFormula (6), formed of the compound represented by Formula (6) and thecompound represented by Formula (9), formed of the compound representedby Formula (1) and the compound represented by Formula (10), or formedof the compound represented by Formula (1) and the compound representedby Formula (9).

In a case where the mixture of organic solvents contained in thechemical liquid is formed of a lactone compound and the compoundrepresented by Formula (5), the chemical liquid does not have desiredperformance. Specifically, in a case where a substrate is coated withsuch a chemical liquid and then coated with a resist composition so asto obtain a predetermined thickness, the thickness of the formed resistfilm tends to be significantly uneven (desired film thicknesscontrollability is not obtained). Furthermore, in a case where a patternis formed by the method described in Examples by using the chemicalliquid, the amount of residues in an unexposed portion and the number ofBRIDGE defects tend to increase. The number of BRIDGE defects will bedescribed later.

In a case where the mixture of organic solvents contained in thechemical liquid is formed the cyclic ketone compound with 6 or moremembers that may have a substituent and the compound represented byFormula (1), and a pattern is formed using the chemical liquid by themethod described in Examples, the amount of residues in an unexposedportion and the number of BRIDGE defects tend to increase.

Furthermore, in a case where the mixture of organic solvents containedin the chemical liquid is formed of a lactone compound, the compoundrepresented by Formula (1), and the compound represented by Formula (5),and a substrate is coated with the chemical liquid and then coated witha resist composition so as to obtain a predetermined thickness, thethickness of the formed resist film tends to be significantly uneven(desired film thickness controllability is not obtained).

In addition, in a case where the mixture of organic solvents containedin the chemical liquid is formed of the compound represented by Formula(1) and the compound represented by Formula (3), and a substrate iscoated with the chemical liquid and then with a resist composition so asto obtain a predetermined thickness, the thickness of the formed resistfilm tends to be significantly uneven (desired film thicknesscontrollability is not obtained).

The mixture of organic solvents contained in the chemical liquid that isformed of the compound represented by Formula (1) and the compoundrepresented by Formula (3) means a mixture formed of two kinds oforganic solvents one of which is the compound represented by Formula (1)and the other is the compound represented by Formula (3).

That is, a combination of propylene glycol monomethyl ether acetate andethyl lactate and a combination of propylene glycol monomethyl etheracetate and 2-hydroxymethyl isobutyrate are included in theaforementioned mixture. In contrast, a mixture of propylene glycolmonomethyl ether acetate, ethyl lactate, and 2-hydroxymethyl isobutyrateis not included in the aforementioned mixture because this mixture isformed of three kinds of organic solvents.

Accordingly, the present invention does not include a chemical liquidcontaining a mixture formed of a lactone compound and the compoundrepresented by Formula (5), a chemical liquid containing a mixtureformed of the cyclic ketone compound with 6 or more members that mayhave a substituent and the compound represented by Formula (1), and achemical liquid containing a mixture formed of a lactone compound, thecompound represented by Formula (1), and the compound represented byFormula (5), and the chemical liquid containing a mixture formed of thecompound represented by Formula (1) and the compound represented byFormula (3).

In view of obtaining a chemical liquid having further improved effectsof the present invention, it is preferable that the chemical liquidaccording to the above embodiment contains a mixture of two or morekinds of the organic solvents described above.

In this case, particularly, advantages such as the improvement ofrobustness of treatment conditions relating to resist saving propertiesand defect inhibition performance can be obtained. Furthermore, theeffects of the present invention can be exerted on various types ofresist solutions.

In the present specification, in a case where a chemical liquid isdescribed as “containing a mixture of organic solvents described above”,the chemical liquid is regarded as including an aspect in which thechemical liquid contains a byproduct, an isomer, an impurity, and thelike that are unintentionally incorporated into the organic solvents.

The chemical liquid containing a mixture formed of MMP and PGMEA hasfurther improved effects of the present invention. Particularly, in acase where the content of MMP in the mixture with respect to the totalmass of the mixture is greater than 5% by mass, the chemical liquid hasparticularly improved resist saving properties. The upper limit of thecontent of MMP in the mixture is not particularly limited, but ispreferably equal to or smaller than 99% by mass in general. It ispreferable that the chemical liquid substantially does not containmoisture.

The chemical liquid containing a mixture formed of MMP and PGME hasfurther improved effects of the present invention. Particularly, in acase where the content of MMP in the mixture with respect to the totalmass of the mixture is greater than 30% by mass, the chemical liquid hasparticularly improved resist saving properties. The upper limit of thecontent of MMP in the mixture is not particularly limited, but ispreferably equal to or smaller than 99% by mass in general. It ispreferable that the chemical liquid substantially does not containmoisture.

[Other Aspects of Chemical Liquid]

The chemical liquid according to a second embodiment of the presentinvention is a chemical liquid containing a mixture of two or more kindsof organic solvents. The mixture contains at least one kind ofcombination among the combinations 1 to 10 of organic solvents describedbelow.

[Mixture of Two or More Kinds of Organic Solvents]

The chemical liquid contains a mixture of two or more kinds of organicsolvents.

The content of the mixture in the chemical liquid is not particularlylimited, but is preferably 99.9% to 100% by mass in general with respectto the mass of the chemical liquid.

Combination 1

γ-Butyrolactone (GBL) and at least one kind of organic solvent selectedfrom the group consisting of cyclopentanone (CyPn), butyl acetate (nBA),ethyl lactate (EL), 2-hydroxymethyl isobutyrate (HBM), cyclopentanonedimethyl acetal (DBCPN), anisole, phenetole, ethylene glycol monomethylether acetate (EGMEA), 3-methoxymethyl propionate (MMP), and3-ethoxyethyl propionate (EEP)

Combination 2

Dimethyl sulfoxide (DMSO) and at least one kind of organic solventselected from the group consisting of propylene glycol monomethyl ether(PGME), CyPn, nBA, propylene glycol monomethyl ether acetate (PGMEA),cyclohexanone (CyHx), EL, HBM, DBCPN, anisole, phenetole, EGMEA, MMP,and EEP

Combination 3

Ethylene carbonate (EC) and at least one kind of organic solventselected from the group consisting of PGME, CyPn, nBA, PGMEA, CyHx, EL,HBM, DBCPN, anisole, phenetole, EGMEA, MMP, and EEP

Combination 4

Propylene carbonate (PC) and at least one kind of organic solventselected from the group consisting of PGME, CyPn, nBA, PGMEA, CyHx, EL,HBM, DBCPN, anisole, phenetole, EGMEA, MMP, and EEP

Combination 5

1-Methyl-2-pyrrolidone (NMP) and at least one kind of organic solventselected from the group consisting of PGME, CyPn, nBA, PGMEA, CyHx, EL,HBM, DBCPN, anisole, phenetole, EGMEA, MMP, and EEP

Combination 6

PGMEA and at least one kind of organic solvent selected from the groupconsisting of CyPn, nBA, DBCPN, anisole, phenetole, EGMEA, MMP, and EEP

Combination 7

CyHx and at least one kind of organic solvent selected from the groupconsisting of PGME, CyPn, nBA, EL, HBM, DBCPN, anisole, phenetole,EGMEA, MMP, and EEP

Combination 8

EL and at least one kind of organic solvent selected from the groupconsisting of PGME, CyPn, nBA, DBCPN, anisole, phenetole, EGMEA, MMP,and EEP

Combination 9

HBM and at least one kind of organic solvent selected from the groupconsisting of PGME, CyPn, nBA, DBCPN, anisole, phenetole, EGMEA, MMP,and EEP

Combination 10

DBCPN and at least one kind of organic solvent selected from the groupconsisting of PGME, CyPn, nBA, anisole, phenetole, EGMEA, MMP, and EEP

The content of each of the organic solvents in the mixture is notparticularly limited, but is preferably 3% to 97% by mass in general andmore preferably 5% to 95% by mass.

In view of obtaining a chemical liquid having further improved effectsof the present invention, it is preferable that the chemical liquidaccording to the above embodiment contains a mixture of two or morekinds of organic solvents described above.

In this case, particularly, advantages such as the improvement ofrobustness of treatment conditions relating to resist saving propertiesand defect inhibition performance can be obtained. Furthermore, theeffects of the present invention can be exerted on various types ofresist solutions.

[Physical Properties of Chemical Liquid or Mixture]

Next, preferable aspects of the physical properties common to thechemical liquid or the mixture according to the embodiment of thepresent invention will be described. In view of making the chemicalliquid have further improved effects of the present invention, the vaporpressure and the surface tension of the mixture and Hansen solubilityparameters of the organic solvents are preferably within a predeterminedrange. Hereinafter, each of the physical properties will be described.

[Vapor Pressure of Mixture]

The vapor pressure at 25° C. of the mixture of two or more kinds oforganic solvents contained in the chemical liquid is not particularlylimited, but is preferably 150 to 1,200 Pa, more preferably 159 to 1,200Pa, even more preferably 160 to 1,000 Pa, and particularly preferably173 to 1,000 Pa. In a case where the vapor pressure of the mixture is160 to 1,000 Pa, the chemical liquid has further improved defectinhibition performance and resist saving properties.

In the present specification, the vapor pressure of the mixture means avapor pressure calculated by the following method.

First, by using the chemical liquid as a sample, the type and content ofeach of the organic solvents contained in the chemical liquid aremeasured using gas chromatography mass spectrometry. In the presentspecification, an organic solvent means an organic compound whosecontent in the chemical liquid is greater than 10,000 mass ppm withrespect to the total mass of the chemical liquid.

The measurement conditions for the gas chromatography mass spectrometryare as described in Examples.

The mixture is constituted with the organic solvents detected by theaforementioned method. Based on the vapor pressure at 25° C. of each ofthe organic solvents contained in the mixture and the molar fraction ofeach of the organic solvents in the mixture, the vapor pressure of themixture is calculated by the following equation. In the presentspecification, a sign “Σ” means sum.

(Vapor pressure of mixture)=Σ((vapor pressure of each of organicsolvents at 25° C.)×(molar fraction of each of organicsolvents))  Equation:

In view of making the chemical liquid have further improved effects ofthe present invention, it is preferable that the mixture contained inthe chemical liquid contains a first organic solvent having a vaporpressure of 160 to 1,000 Pa at 25° C. and a second organic solventhaving a vapor pressure higher than 1,000 Pa at 25° C. or contains twoor more kinds of first organic solvents.

First Organic Solvent

The first organic solvent is an organic solvent having a vapor pressureof 160 to 1,000 Pa at 25° C. Examples of the first organic solventinclude PGMEA (493), CyHx (507), EL (187), HBM (267), DBCPN (400),anisole (427), phenetole (211), EGMEA (280), MMP (507), EEP (160), andthe like. The numbers in the bracket represent the vapor pressure at 25°C. (unit: Pa).

The content of the first organic solvent in the mixture is notparticularly limited. However, generally, the content of the firstorganic solvent with respect to the total mass of the mixture ispreferably 3% to 100% by mass, more preferably 5% to 97% by mass, andeven more preferably 10% to 95% by mass. In a case where the mixturecontains the second organic solvent, the content of the first organicsolvent is preferably 30% to 80% by mass. One kind of the first organicsolvent may be used singly, or two or more kinds of the first organicsolvents may be used in combination. In a case where two or more kindsof the first organic solvents are used in combination, the total contentof the first organic solvents is preferably within the above range.

Second Organic Solvent

The second organic solvent is an organic solvent having a vapor pressurehigher than 1,000 Pa at 25° C. Examples of the second organic solventinclude nBA (1,200), PGME (1,453), CyPn (1,520), and the like. In viewof obtaining a chemical liquid having further improved effects of thepresent invention, CyPn is preferable. The numbers in the bracketrepresent the vapor pressure at 25° C. (unit: Pa).

The content of the second organic solvent in the mixture is notparticularly limited. However, generally, the content of the secondorganic solvent with respect to the total mass of the mixture ispreferably 20% to 60% by mass. One kind of the second organic solventmay be used singly, or two or more kinds of the second organic solventsmay be used in combination. In a case where two or more kinds of thesecond organic solvents are used in combination, the total content ofthe second organic solvents is preferably within the above range.

In view of making the chemical liquid have further improved effects ofthe present invention, it is preferable that the mixture contained inthe chemical liquid contains a third organic solvent having a vaporpressure lower than 160 Pa at 25° C.

Particularly, in view of obtaining a chemical liquid having furtherimproved effects of the present invention, the mixture contained in thechemical liquid preferably contains at least one kind of the thirdorganic solvent and at least one kind of the first organic solvent orcontains at least one kind of the third organic solvent and at least onekind of the second organic solvent, more preferably contains at leastone kind of the third organic solvent and at least one kind of the firstorganic solvent, even more preferably contains at least one kind of thethird organic solvent and at least one kind of the first organicsolvent, and particularly preferably contains at least one kind of thethird organic solvent and at least one kind of the first organicsolvent.

Third Organic Solvent

The third organic solvent means an organic solvent having a vaporpressure lower than 160 Pa at 25° C.

Examples of such an organic solvent include GBL (147), DMSO (13), PC(53), EC (67), NMP (40), and the like, but the third organic solvent isnot limited to these. The numbers in the bracket represent the vaporpressure (Pa) at 25° C.

The content of the third organic solvent in the mixture is notparticularly limited. However, generally, the content of the thirdorganic solvent with respect to the total mass of the mixture ispreferably equal to or smaller than 50% by mass, more preferably lessthan 35% by mass, even more preferably less than 10% by mass, andparticularly preferably equal to or smaller than 5% by mass. The lowerlimit of the content of the third organic solvent is not particularlylimited, but is preferably equal to or greater than 0.01% by mass ingeneral.

One kind of the third organic solvent may be used singly, or two or morekinds of the third organic solvents may be used in combination. In acase where two or more kinds of the third organic solvents are used incombination, the total content thereof is preferably within the aboverange.

[Surface Tension of Mixture]

The surface tension at 25° C. of the mixture of two or more kinds oforganic solvents contained in the chemical liquid is preferably equal toor higher than 28 mN/m, more preferably higher than 29 mN/m, and evenmore preferably equal to or higher than 30 mN/m. The upper limit of thesurface tension is not particularly limited, but is preferably equal toor lower than 45 mN/m in general, more preferably equal to or lower than42 mN/m, and even more preferably equal to or lower than 40 mN/m.

In a case where the surface tension of the mixture is equal to or higherthan 28 mN/m, the chemical liquid has further improved defect inhibitionperformance (particularly, BRIDGE defect inhibition performance). In acase where the surface tension of the mixture is higher than 29 mN/m,the chemical liquid has further improved effects of the presentinvention.

In the present specification, the surface tension means a surfacetension calculated by the following method.

First, by using the chemical liquid as a sample, the type and content ofeach of the organic solvents contained in the chemical liquid aremeasured using gas chromatography mass spectrometry.

The measurement conditions for the gas chromatography mass spectrometryare as described in Examples.

The mixture is constituted with the organic solvents detected by theaforementioned method. Based on the surface tension at 25° C. of each ofthe organic solvents contained in the mixture and a molar fraction ofeach of the organic solvents in the mixture, the surface tension of themixture is calculated by the following equation.

(Surface tension of mixture)=Σ((surface tension of each of organicsolvents at 25° C.)×(molar fraction of each of organicsolvents))  Equation:

[Hansen Solubility Parameter of Organic Solvent]

In view of making the chemical liquid have further improved effects ofthe present invention, it is preferable that the mixture contains aspecific organic solvent having a Hansen solubility parameter higherthan 9.5 (MPa)^(0.5) in terms of a hydrogen bond element (hereinafter,referred to as “δh” as well in the present specification) or having aHansen solubility parameter higher than 15.5 (MPa)^(0.5) in terms of adispersion element (hereinafter, referred to as “δd” as well in thepresent specification).

In the present specification, Hansen solubility parameters mean thosedescribed in “Hansen Solubility Parameters: A Users Handbook” (SecondEdition, pp. 1-310, CRC Press, 2007), and the like. That is, Hansensolubility parameters describe solubility by using multi-dimensionalvectors (a dispersion element (δd), a dipole-dipole force element (δp),and a hydrogen bond element (δh)). These three parameters can beconsidered as coordinates of points in a three-dimensional space calledHansen space.

δh of the specific organic solvent is preferably higher than 9.5(MPa)^(0.5), and more preferably higher than 11 (MPa)^(0.5). The upperlimit of δh is not particularly limited, but is preferably equal to orlower than 15 (MPa)^(0.5) in general.

δd of the specific organic solvent is preferably higher than 15.5(MPa)^(0.5), and more preferably equal to or higher than 17 (MPa)^(0.5).The upper limit of δd is not particularly limited, but is preferablyequal to or lower than 20 (MPa)^(0.5).

Examples of the specific solvent include DBCPN (4.2, 16.6), HBM (12.2,16.5), EL (12.5, 16.0), CyHx (5.1, 17.8), PGMEA (9.8, 15.6), CyPN (4.8,17.8), GBL (7.0, 17.4), DMSO (10.2, 18.4), PC (6.5, 17.3), EC (8.0,18.1), NMP (7.2, 18.0), and the like. The numbers in the bracketrepresent Hansen solubility parameters (δh and δd), and the unit thereofis (MPa)^(0.5).

Examples of the combination of the organic solvents contained in themixture include the following combinations, but the present invention isnot limited thereto. The numbers in the bracket represent the content (%by mass) of each of the organic solvents with respect to the total massof the mixture.

Examples of the combination include GBL(5)/DBCPN(95), GBL(5)/HBM(95),GBL(5)/EL(95), GBL(50)/CyPn(50), GBL(50)/nBA(50), DMSO(5)/HBM(95),DMSO(5)/EL(95), DMSO(30)/CyHx(70), DMSO(30)/PGMEA(70), DMSO(40)/nBA(60),DMSO(50)/PGME(50), DMSO(50)/CyPn(50), PC(5)/CyHx(95), PC(5)/HBM(95),PC(5)/EL(95), PC(20)/PGMEA(80), PC(20)/DBCPN(80), PC(50)/PGME(50),PC(50)/CyPn(50), EC(5)/HBM(95), EC(5)/EL(95), EC(20)/CyHx(80),EC(20)/PGMEA(80), EC(50)/PGME(50), EC(50)/CyPn(50), NMP(5)/HBM(95),NMP(5)/EL(95), NMP(20)/CyHx(80), NMP(20)/PGMEA(80), NMP(20)/DBCPN(80),NMP(50)/PGME(50), NMP(50)/CyPn(50), PGMEA(80)/CyPn(20),CyHx(80)/CyPn(20), CyHx(80)/EL(20), CyHx(80)/HBM(20),CyHx(80)/DBCPN(20), EL(70)/PGME(30), EL(70)/CyPn(30), EL(20)/DBCPN(80),EL(40)/HBM(60), HBM(80)/PGME(20), HBM(80)/CyPn(20), HBM(80)/DBCPN(20),DBCPN(80)/PGME(20), DBCPN(80)/CyPn(20), PGMEA(80)/CyPn(20),PGMEA(70)/EL(10)/CyPn(30), CyHx(80)/PGMEA(60)/CyPn(20),DBCPN(80)/EL(30)/CyPn(20), DMSO(10)/HBM(35)/PGMEA(55),DMSO(5)/EL(45)/CyPn(50), DMSO(5)/HBM(25)/CyHx(70),DMSO(5)/HBM(25)/DBCPN(70), GBL(5)/HBM(35)/PGMEA(60),GBL(10)/HBM(35)/PGMEA(55), GBL(20)/HBM(35)/PGMEA(45),GBL(25)/HBM(35)/PGMEA(40), GBL(30)/HBM(35)/PGMEA(35),GBL(10)/EL(30)/CyPn(60), GBL(10)/HBM(25)/CyHx(65),GBL(10)/HBM(25)/DBCPN(65), EC(10)/HBM(45)/PGMEA(45),EC(10)/EL(30)/CyPn(60), EC(10)/HBM(25)/CyHx(65),EC(10)/HBM(25)/DBCPN(65), MMP(95)/DMSO(5), MMP(97)/DMSO(3),MMP(95)/PC(5), MMP(97)/PC(3), EGMEA(50)/PGMEA(50), EGMEA(50)/EL(50),EGMEA(80)/DBCPN(20), EGMEA(80)/PGME(20), EGMEA(90)/GBL(10),EGMEA(90)/DMSO(10), EGMEA(90)/PC(10), MMP(50)/PGMEA(50), MMP(50)/EL(50),MMP(80)/DBCPN(20), MMP(80)/PGME(20), MMP(90)/GBL(10), MMP(90)/DMSO(10),MMP(90)/PC(10), EEP(30)/EL(70), and the like.

[Use of Chemical Liquid]

The chemical liquid according to the above embodiment is preferably usedfor manufacturing semiconductors. Specifically, in a semiconductordevice manufacturing process including a lithography step, an etchingstep, an ion implantation step, a peeling step, and the like, thechemical liquid is used for treating an organic substance after eachstep is finished or before the next step is started. Specifically, thechemical liquid is suitably used as a prewet solution, a developer, arinsing solution, a peeling solution, and the like.

Furthermore, the chemical liquid can also be used as a diluent of aresin contained in a resist solution (which will be described later). Inaddition, the chemical liquid may be diluted with another organicsolvent and/or water, and the like.

The chemical liquid can also be suitably used for other uses in additionto the manufacturing of semiconductors. The chemical liquid can be usedas a developer or a rinsing solution of polyimide, a resist for asensor, a resist for a lens, and the like.

In addition, the chemical liquid can also be used as a solvent formedical uses or for washing. Particularly, the chemical liquid can besuitably used for washing containers, piping, substrates (for example, awafer and glass), and the like.

Particularly, the chemical liquid according to the above embodiment ismore preferably used for pre-wetting. That is, it is preferable that thechemical liquid according to the above embodiment is used as a prewetsolution.

The chemical liquid can be used for pre-wetting and for rinsing the edgeof a wafer before or after resist coating.

Furthermore, in a case where a substrate (wafer) is coated with a Bottomof AntiReflection Coating (BARC) composition before being coated with anactinic ray-sensitive or radiation-sensitive resin composition, it isalso possible to remove the BARC composition, with which the edgeportion of the wafer is unintentionally coated, by using the chemicalliquid.

[Manufacturing Method of Chemical Liquid]

As the manufacturing method of the chemical liquid, known manufacturingmethods can be used without particular limitation. Examples of themanufacturing method of the chemical liquid include a manufacturingmethod including a step of preparing organic solvents and a step ofmixing together the organic solvents so as to obtain a mixture. Themanufacturing method may additionally include a step of purifying theorganic solvents and/or the mixture by using a filter or the like.Furthermore, the manufacturing method may additionally include anelectricity removing step of removing the electricity from the organicsolvents and/or the mixture so as to reduce the charge potentialthereof.

As the organic solvents used for manufacturing the chemical liquid, itis preferable to prepare organic solvents in which the content of animpurity is small. Examples of commercial products of such organicsolvents include those called “high-purity grade products”.

Examples of the method for purifying the organic solvents and/or themixture include methods such as distillation, filtration, and the like.As a distillation device and a filtration device, known devices can beused.

<Container>

The chemical liquid may be temporarily stored in a container until thechemical liquid is used. As the container for storing the chemicalliquid, known containers can be used without particular limitation.

As the container storing the chemical liquid, a container formanufacturing semiconductors is preferable which has a high internalcleanliness and hardly causes elution of impurities.

Examples of the usable container specifically include a “CLEAN BOTTLE”series manufactured by AICELLO CORPORATION, “PURE BOTTLE” manufacturedby KODAMA PLASTICS Co., Ltd., and the like, but the container is notlimited to these.

As the container, for the purpose of preventing mixing of impuritiesinto the chemical liquid (contamination), it is preferable to use acontainer in which the inner wall of the container has a 6-layerstructure formed of 6 kinds of resins or has a 7-layer structure formedof 6 kinds of resins. Examples of these containers include thecontainers described in JP2015-123351A.

It is preferable in the container, the device used for manufacturing thechemical liquid, and the member (filter or the like) used formanufacturing the chemical liquid, the portions (the inner wall of thecontainer, the inner wall of the device, the interior of the member, andthe like; hereinafter, referred to as “liquid contact portion” as well)that contact the chemical liquid are washed before the container, thedevice, and the member are used. As a liquid used for washing, a washingsolution containing few impurities is preferable. As the washingsolution, for example, “high-purity grade products” described above,solutions obtained by purifying the high-purity grade products, thechemical liquid, a solution obtained by diluting the chemical liquid,and the like are preferable. At the time of washing the liquid contactportion of the device used for manufacturing the chemical liquid byusing a washing solution, it is preferable that the liquid contactportion is washed until the amount of impurities contained in thewashing solution becomes equal to or smaller than a predetermined amount(preset value). After being manufactured, the chemical liquid may bebottled using a container such as a gallon bottle or a quart bottle,transported, and stored. The gallon bottle may be formed of a glassmaterial or other materials.

In order to prevent the change of the components in the solution duringstorage, purging may be performed in the interior of the container byusing an inert gas (nitrogen, argon, or the like) having a purity equalto or higher than 99.99995% by volume. Particularly, a gas with smallmoisture content is preferable. The temperature at the time of transportand storage may be room temperature. However, in order to preventalteration, the temperature may be controlled within a range of −20° C.to 30° C.

(Clean Room)

It is preferable that all of the manufacturing of the chemical liquid,the opening and/or washing of the container, the handling includingstorage of the solution, the treatment and analysis, and the measurementare performed in a clean room. It is preferable that the clean roommeets the 14644-1 clean room standard. The clean room preferably meetsany of International Organization for Standardization (ISO) class 1, ISOclass 2, ISO class 3, or ISO class 4, more preferably meets ISO class 1or ISO class 2, and even more preferably meets ISO class 1.

[Pattern Forming Method]

It is preferable that the chemical liquid is used for forming a resistpattern (hereinafter, simply referred to as “pattern”) used formanufacturing semiconductors. The pattern forming method in which thechemical liquid is used is not particularly limited, and examplesthereof include known pattern forming methods.

Particularly, it is preferable that the pattern forming method includesthe following steps.

(A) Pre-wetting step of coating substrate with chemical liquid so as toobtained pre-wetted substrate

(B) Resist film forming step of forming resist film on pre-wettedsubstrate by using actinic ray-sensitive or radiation-sensitive resincomposition

(C) Exposure step of exposing resist film

(D) Development step of developing exposed resist film by usingdeveloper Hereinafter, the aspect of each of the steps will bedescribed.

[(A) Pre-Wetting Step]

The pre-wetting step is a step of coating a substrate with the chemicalliquid.

As the substrate, know substrates used for manufacturing semiconductorscan be used without particular limitation. Examples of the substrateinclude an inorganic substrate such as silicon, SiO₂, or SiN, acoating-type inorganic substrate such as Spin On Glass (SOG), and thelike, but the substrate is not limited to these.

Furthermore, the substrate may be a substrate with an antireflectionfilm comprising an antireflection film. As the antireflection film,known organic or inorganic antireflection films can be used withoutparticular limitation.

As the method for coating the substrate with the chemical liquid, knowncoating methods can be used without particular limitation. Particularly,as the coating method, spin coating is preferable because this methodmakes it possible to form a uniform resist film by using smaller amountsof the actinic ray-sensitive or radiation-sensitive resin composition inthe resist film forming step which will be described later.

As the method for coating the substrate with the chemical liquid, knowncoating methods can be used without particular limitation. Particularly,as the coating method, spin coating is preferable because this methodmakes it possible to form a uniform resist film by using smaller amountsof the actinic ray-sensitive or radiation-sensitive resin composition inthe resist film forming step which will be described later.

The thickness of a chemical liquid layer formed on the substrate byusing the chemical liquid is not particularly limited. Generally, thethickness of the chemical liquid layer is preferably 0.001 to 10 μm, andmore preferably 0.005 to 5 μm.

Provided that a resist solution, with which the substrate is to becoated, is a resist for ArF immersion exposure, and that the surfacetension of the resist solution is 28.8 mN/m, although the surfacetension of the mixture in the chemical liquid is not particularlylimited, it is preferable to supply the chemical liquid to the wafer asa prewet solution by making the surface tension of the chemical liquidbecome higher than the surface tension of the resist solution.

Generally, the chemical liquid is supplied to the wafer by a method ofmoving a prewet nozzle to a position above the central portion of thewafer. Then, by opening or closing a valve, the chemical liquid issupplied to the wafer.

In a state where the wafer stands still, a predetermined amount of thechemical liquid is supplied to the central portion of the wafer from theprewet nozzle. Then, the wafer is rotated at a first speed V1 which is,for example, about 500 rotation per minute (rpm) such that the chemicalliquid on the wafer spreads over the entire surface of the wafer. As aresult, the entire surface of the wafer is wet with the chemical liquid.

The upper limit of the first speed V1 is not particularly limited, butis preferably equal to or lower than 3,000 rpm.

Thereafter, the valve of a line connected to a resist solution isopened. As a result, the resist solution starts to be jetted from aresist nozzle, and the resist solution starts to be supplied to thecentral portion of the wafer. In this way, (B) resist film forming step(which will be described later) is started.

In the resist film forming step, from the first speed V1, the rotationspeed of the wafer is increased to a high speed which is a second speedV2 of about 2,000 to 4,000 rpm for example. The wafer rotating at thefirst speed V1 before the start of the resist film forming step is thengradually accelerated such that the speed continuously and smoothlychanges. At this time, the acceleration of the rotation of the wafer isgradually increased from zero, for example. At the time when the resistfilm forming step ends, the acceleration of the rotation of the wafer isreduced such that the rotation speed of the wafer W smoothly reaches thesecond speed V2. In this way, during the resist film forming step, therotation speed of the wafer changes such that the transition from thefirst speed V1 to the second speed V2 is represented by an S-shapedcurve. In the resist film forming step, due to the centrifugal force,the resist solution supplied to the central portion of the wafer spreadsover the entire surface of the wafer, whereby the surface of the waferis coated with the resist solution.

The technique for saving resist by changing the rotation speed of awafer at the time of resist coating is specifically described inJP2009-279476A.

The interval between a point in time when (A) pre-wetting step hasfinished and a point in time when resist solution coating in (B) resistfilm forming step is started is not particularly limited, but ispreferably equal to or shorter than 7 seconds in general.

The chemical liquid may be recycled. That is, the chemical liquid usedin the pre-wetting step can be recovered and reused in the pre-wettingstep for other wafers.

In a case where the chemical liquid is recycled, it is preferable toadjust the content of the impurity metal, the organic impurity, water,and the like contained in the recovered chemical liquid. The adjustmentmethod is as described above regarding the manufacturing method of thechemical liquid.

<Affinity Between Chemical Liquid and Resin>

Regarding the affinity between the chemical liquid used in thepre-wetting step and the actinic ray-sensitive or radiation-sensitiveresin composition which will be described later, there is no particularlimitation. However, in view of making it possible to form a moreuniform resist film by using smaller amounts of the actinicray-sensitive or radiation-sensitive resin composition, it is preferablethat the chemical liquid and the resin contained in the actinicray-sensitive or radiation-sensitive resin composition satisfy thefollowing relationship (in a case where the actinic ray-sensitive orradiation-sensitive resin composition contains two or more kinds ofresins, “mixture” of the resins is regarded as the resin; the contentmass ratio of each of the resins in the mixture is the same as thecontent mass ratio of each of the resins in the actinic ray-sensitive orradiation-sensitive resin composition with respect to the total mass ofthe resins; the above resins do not include a hydrophobic resin whichwill be described later).

The chemical liquid and the resin preferably satisfy the followingcondition 1 and condition 2 at 25° C. In a case where the chemicalliquid satisfies the following condition 1 and condition 2 at 25° C., itis possible to form a more uniform resist film by using smaller amountsof the actinic ray-sensitive or radiation-sensitive resin composition.

(Condition 1)

Rsq1 calculated by Equation 1 based on a proton spin-spin relaxationtime measured for a chemical liquid and a first test solution formed ofa resin and the chemical liquid by using a pulsed nuclear magneticresonance-type particle interface characteristic evaluator is higherthan 0.5.

Rsq1=(τ0/τ1)−1  (Equation 1)

In Equation 1, τ0 represents a spin-spin relaxation time of the chemicalliquid, and t 1 represents a spin-spin relaxation time of the first testsolution. The resin contained in the first test solution is regarded asbeing dissolved in the chemical liquid.

Details of Condition 1 will be described.

First, the pulsed nuclear magnetic resonance-type particle interfacecharacteristic evaluator is an evaluator adopting a method of observingthe state of spin (magnetism) of a target. Examples of the pulsednuclear magnetic resonance-type particle interface characteristicevaluator include “Acorn Area” manufactured by Xigo Nanotools, and thelike.

The aforementioned evaluator measures a time (spin-spin relaxation time)taken for a measurement target to return to the normal state immediatelyafter the application of energy thereto (excitation state). In the testsolution (first test solution) in which the resin is dissolved in thechemical liquid, the spin-spin relaxation time changes by being affectedby the type of organic solvent in the chemical liquid contacting theresin and the like.

It is unclear why the above change occurs. Presumably, this is becausethe amount of molecules of the organic solvent contacting the resinaffects the spin-spin relaxation time.

It is considered that the amount of molecules of the organic solventcontacting the resin may change by being affected by the surface area ofthe resin, the wettability between the organic solvent and the resin,and the like. That is, presumably, the amount of the organic solventmolecules may reflect the strength of the interaction between the resinand the chemical liquid.

Rsq1 calculated by Equation 1 based on a proton spin-spin relaxationtime is a parameter showing the compatibility between a resin and achemical liquid.

Rsq1=(τ0/τ1)−1  (Equation 1)

It is preferable that Rsq1 is higher than 0.5. In a case where Rsq1 ishigher than 0.5, the chemical liquid and the resin exhibit highercompatibility. The upper limit of Rsq1 is not particularly limited, butis preferably equal to or lower than 10.0 in general.

(Condition 2)

SRsq calculated by Equation 2 based on a proton spin-spin relaxationtime measured for a second test solution, which is formed of the resinand the chemical liquid and in which the content of the resin isdifferent from the content of the resin in the first test solution, andthe first test solution by using a pulsed nuclear magneticresonance-type particle interface characteristic evaluator is higherthan −1.

SRsq=(Rsq2−Rsq1)/(c2−c1)  (Equation 2)

In Equation 2, Rsq1 represents a value calculated by Equation 1, andRsq2 represents a value calculated by Equation 3. c1 and c2 representthe mass-based content of the resin in the first test solution and thesecond test solution respectively. The unit of the mass-based content is% by mass, and c2>c1. The resin contained in the first test solution andthe second test solution is regarded as being dissolved in the chemicalliquid.

Rsq2=(τ0/τ2)−1  (Equation 3)

In Equation 3, τ0 has the same definition as TO in Equation 1, and τ2represents a spin-spin relaxation time of the second test solution.

Details of Condition 2 will be described.

In Equation 2, c1 and c2 represent the content of the resin (% by mass)in the first test solution and the second test solution respectively. Aslong as the resin is thoroughly dissolved in the first test solution andthe second test solution, c1 and c2 are not particularly limited. Forexample, c1 may be 0.5% by mass, and c2 may be 3.0% by mass or the like.

SRsq represents a rate of change of Rsq in a predetermined concentrationrange (c2−c1). SRsq is preferably higher than −1, and more preferablyequal to or higher than −0.8. The upper limit of SRsq is notparticularly limited, but is preferably equal to or lower than 10 ingeneral. In a case where SRsq is higher than −1, the resin tends toremain more homogeneously dispersed in the chemical liquid, and itbecomes more difficult for the resin to be aggregated.

[(B) Resist Film Forming Step]

The resist film forming step is a step of forming a resist film on thepre-wetted substrate (substrate comprising a chemical liquid layer) byusing an actinic ray-sensitive or radiation-sensitive resin composition.Hereinafter, first, aspects of the actinic ray-sensitive orradiation-sensitive resin composition will be described.

<Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition>

As the actinic ray-sensitive or radiation-sensitive resin compositionwhich can be used in the resist film forming step, known actinicray-sensitive or radiation-sensitive resin compositions can be usedwithout particular limitation.

It is preferable that the actinic ray-sensitive or radiation-sensitiveresin composition (hereinafter, referred to as “resist composition” aswell) contains a resin (hereinafter, referred to as “acid-decomposableresin” as well in the present specification), which contains a repeatingunit containing a group generating a polar group (a carboxyl group, aphenolic hydroxyl group, or the like) by being decomposed by the actionof an acid, and a compound (hereinafter, referred to as “photoacidgenerator” as well in the present specification) which generates an acidby the irradiation of actinic rays or radiation.

Particularly, in view of obtaining further improved effects of thepresent invention, the following resist compositions are preferable.

-   -   Resist composition containing resin represented by Formula (I)        which will be described later    -   Resist composition containing acid-decomposable resin having        phenolic hydroxyl group which will be described later    -   Resist composition containing hydrophobic resin, which will be        described later, and acid-decomposable resin

Hereinafter, each of the components of the resist compositions will bedescribed.

(Acid-Decomposable Resin)

In an acid-decomposable group, a polar group is protected with a groupdissociated by an acid (acid-dissociable group). Examples of theacid-dissociable group include —C(R₃₆)(R₃₇)(R₃₈), —C(R₃₆)(R₃₇)(OR₃₉),—C(R₀₁)(R₀₂)(OR₃₉), and the like.

In the formulae, R₃₆ to R₃₉ each independently represent an alkyl group,a cycloalkyl group, an aryl group, an aralkyl group, or an alkenylgroup. R₃₆ and R₃₇ may form a ring by being bonded to each other.

R₁₀ and R₀₂ each independently represent a hydrogen atom, an alkylgroup, a cycloalkyl group, an aryl group, an aralkyl group, or analkenyl group.

Examples of the acid-decomposable resin include a resin P having anacid-decomposable group represented by Formula (AI).

In Formula (AI), Xa₁ represents a hydrogen atom or an alkyl group whichmay have a substituent.

T represents a single bond or a divalent linking group.

Ra₁ to Ra₃ each independently represent an alkyl group (linear orbranched) or a cycloalkyl group (monocyclic or polycyclic).

Two out of R₁ to Ra₃ may form a cycloalkyl group (monocyclic orpolycyclic) by being bonded to each other.

Examples of the alkyl group represented by Xa₁ which may have asubstituent include a methyl group and a group represented by —CH₂—R₁₁.R₁₁ represents a halogen atom (a fluorine atom or the like), a hydroxylgroup, or a monovalent organic group.

Xa₁ is preferably a hydrogen atom, a methyl group, a trifluoromethylgroup, or a hydroxymethyl group.

Examples of the divalent linking group represented by T include analkylene group, a —COO-Rt- group, a —O-Rt- group, and the like. In theformula, Rt represents an alkylene group or a cycloalkylene group.

T is preferably a single bond or a —COO-Rt- group. Rt is preferably analkylene group having 1 to 5 carbon atoms, and more preferably a —CH₂—group, a —(CH₂)₂— group, or a —(CH₂)₃— group.

The alkyl group represented by R₁ to Ra₃ preferably has 1 to 4 carbonatoms.

The cycloalkyl group represented by R₁ to Ra₃ is preferably a monocycliccycloalkyl group such as a cyclopentyl group or a cyclohexyl group or apolycyclic cycloalkyl group such as a norbornyl group, atetracyclodecanyl group, a tetracyclododecanyl group, or an adamantylgroup.

The cycloalkyl group formed by bonding of two groups out of Ra₁ to Ra₃is preferably a monocyclic cycloalkyl group such as a cyclopentyl groupor a cyclohexyl group or a polycyclic cycloalkyl group such as anorbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group,or an adamantyl group, and more preferably a monocyclic cycloalkyl grouphaving 5 or 6 carbon atoms.

In the cycloalkyl group formed by bonding of two groups out of Ra₁ toRa₃, for example, one methylene group constituting the ring may besubstituted with a heteroatom such as an oxygen atom or a group having aheteroatom such as a carbonyl group.

As the repeating unit represented by Formula (AI), for example, anaspect is preferable in which Ra₁ is a methyl group or an ethyl group,and Ra₂ and Ra₃ form the aforementioned cycloalkyl group by being bondedto each other.

Each of the above groups may have a substituent. Examples of thesubstituent include an alkyl group (having 1 to 4 carbon atoms), ahalogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbonatoms), a carboxy group, an alkoxycarbonyl group (having 2 to 6 carbonatoms), and the like. The number of carbon atoms in the substituent ispreferably equal to or smaller than 8.

The total content of the repeating unit represented by Formula (AI) withrespect to all the repeating units in the resin P is preferably 20 to 90mol %, more preferably 25 to 85 mol %, and even more preferably 30 to 80mol %.

Specific examples of the repeating unit represented by Formula (AI) willbe shown below, but the present invention is not limited thereto.

In the specific examples, Rx and Xa₁ each independently represent ahydrogen atom, CH₃, CF₃, or CH₂OH. Rxa and Rxb each represent an alkylgroup having 1 to 4 carbon atoms. Z represents a substituent containinga polar group. In a case where there is a plurality of Z's, Z's areindependent from each other. p represents 0 or a positive integer.Examples of the substituent represented by Z containing a polar groupinclude a hydroxyl group, a cyano group, an amino group, an alkyl amidegroup, a sulfonamide group, and a linear or branched alkyl group orcycloalkyl group having these groups.

(Repeating Unit Having Lactone Structure)

It is preferable that the resin P contains a repeating unit Q having alactone structure.

The repeating unit Q having a lactone structure preferably has a lactonestructure on a side chain. For example, the repeating unit Q is morepreferably a repeating unit derived from a (meth)acrylic acid derivativemonomer.

One kind of repeating unit Q having a lactone structure may be usedsingly, or two or more kinds of repeating units Q may be used incombination. It is preferable to use one kind of repeating unit Q.

The content of the repeating unit Q having a lactone structure withrespect to all the repeating units in the resin P is, for example, 3 to80 mol %, and preferably 3 to 60 mol %.

The lactone structure is preferably a 5- to 7-membered lactonestructure, and more preferably a structure in which another ringstructure is fused with a 5- to 7-membered lactone structure by forminga bicyclo structure or a spiro structure.

It is preferable that the lactone structure has a repeating unit havinga lactone structure represented by any of Formulae (LC1-1) to (LC1-17).As the lactone structure, a lactone structure represented by Formula(LC1-1), Formula (LC1-4), Formula (LC1-5), or Formula (LC1-8) ispreferable, and a lactone structure represented by Formula (LC1-4) ismore preferable.

The lactone structure portion may have a substituent (Rb₂). As thesubstituent (Rb₂), for example, an alkyl group having 1 to 8 carbonatoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy grouphaving 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbonatoms, a carboxy group, a halogen atom, a hydroxyl group, a cyano group,an acid-decomposable group, and the like are preferable. n₂ representsan integer of 0 to 4. In a case where n₂ is equal to or greater than 2,a plurality of substituents (Rb₂) may be the same as or different fromeach other, and a plurality of substituents (Rb₂) may form a ring bybeing bonded to each other.

The resin P is preferably a resin including a repeating unit selectedfrom the group consisting of a repeating unit represented by Formula(a), a repeating unit represented by Formula (b), a repeating unitrepresented by Formula (c), a repeating unit represented by Formula (d),and a repeating unit represented by Formula (e) (hereinafter, this resinwill be referred to as “resin represented by Formula (I)” as well).

The resin represented by Formula (I) is a resin whose solubility in adeveloper (chemical liquid which will be described later), whichcontains an organic solvent as a main component is reduced, by theaction of an acid. The resin contains an acid-decomposable group. In thechemical liquid, the resin represented by Formula (I) is excellentlydissolved. Therefore, the chemical liquid makes it easy to obtain auniform resist film by using smaller amounts of the resist composition.Hereinafter, the resin represented by Formula (I) will be described.

Resin Represented by Formula (I)

Formula (I) is constituted with a repeating unit (a) (repeating unitrepresented by Formula (a)), a repeating unit (b) (repeating unitrepresented by Formula (b)), a repeating unit (c) (repeating unitrepresented by Formula (c)), a repeating unit (d) (repeating unitrepresented by Formula (d)), and a repeating unit (e) (repeating unitrepresented by Formula (e)).

In Formula (I), R_(x1) to R_(x5) each independently represent a hydrogenatom or an alkyl group which may have a substituent.

R₁ to R₄ each independently represent a monovalent substituent, and p1to p4 each independently represent 0 or a positive integer.

Ra represents a linear or branched alkyl group.

T₁ to T₅ each independently represent a single bond or a divalentlinking group.

R₅ represents a monovalent organic group.

a to e each represent mol %. a to e each independently represent anumber included in a range of 0≤a≤100, 0≤b≤100, 0≤c<100, 0≤d<100, and0≤e<100. Here, a+b+c+d+e=100, and a+b≠0.

In Formula (I), the repeating unit (e) has a structure different fromall of the repeating units (a) to (d).

Examples of the alkyl group represented by R_(x1) to R_(x5) that mayhave a substituent include a methyl group and a group represented by—CH₂—R₁₁. R₁₁ represents a halogen atom (a fluorine atom or the like), ahydroxyl group, or a monovalent organic group.

R_(x1) to R_(x5) preferably each independently represent a hydrogenatom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

Examples of the divalent linking group represented by T₁ to T₅ inFormula (I) include an alkylene group, a —COO-Rt- group, a —O-Rt- group,and the like. In the formula, Rt represents an alkylene group or acycloalkylene group.

T₁ to T₅ preferably each independently represent a single bond or a—COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbonatoms, and more preferably a —CH₂— group, a —(CH₂)₂— group, or a—(CH₂)₃— group.

In Formula (I), Ra represents a linear or branched alkyl group. Examplesthereof include a methyl group, an ethyl group, a t-butyl group, and thelike. Among these, a linear or branched alkyl group having 1 to 4 carbonatoms is preferable.

In Formula (I), R₁ to R₄ each independently represent a monovalentsubstituent. R₁ to R₄ are not particularly limited, and examples thereofinclude a hydroxyl group, a cyano group, and a linear or branched alkylor cycloalkyl group having a hydroxyl group, a cyano group, and thelike.

In Formula (I), p1 to p4 each independently represent 0 or a positiveinteger. The upper limit of p1 to p4 equals the number of hydrogen atomswhich can be substituted in each repeating unit.

In Formula (I), R₅ represents a monovalent organic group. R₅ is notparticularly limited, and examples thereof include a monovalent organicgroup having a sultone structure, a monovalent organic group having acyclic ether such as tetrahydrofuran, dioxane, 1,4-thioxane, dioxolane,and 2,4,6-trioxabicyclo[3.3.0]octane, and an acid-decomposable group(for example, an adamantyl group quaternized by the substitution ofcarbon in a position bonded to a —COO group with an alkyl group).

The repeating unit (b) in Formula (I) is preferably formed of themonomer described in paragraphs [0014] to [0018] in JP2016-138219A.

In Formula (I), a to e each represent mol %. a to e each independentlyrepresent a number included in a range of 0≤a≤100, 0≤b≤100, 0≤c<100,0≤d<100, and 0≤e<100. Here, a+b+c+d+e=100, and a+b≠0.

In Formula (I), a+b (the content of the repeating unit having anacid-decomposable group with respect to all the repeating units) ispreferably 20 to 90 mol %, more preferably 25 to 85 mol %, and even morepreferably 30 to 80 mol %.

Furthermore, in Formula (I), c+d (the content of the repeating unithaving a lactone structure with respect to all the repeating units) ispreferably 3 to 80 mol %, and more preferably 3 to 60 mol %.

One kind of each of the repeating unit (a) to repeating unit (e) may beused singly, or two or more kinds of each of the repeating unit (a) torepeating unit (e) may be used in combination. In a case where two ormore kinds of repeating units are used in combination, the total contentof each repeating unit is preferably within the above range.

The weight-average molecular weight (Mw) of the resin represented byFormula (I) is preferably 1,000 to 200,000 in general, more preferably2,000 to 20,000, and even more preferably 3,000 to 15,000. Theweight-average molecular weight is determined by Gel PermeationChromatography (GPC) by using tetrahydrofuran (THF) as a developingsolvent, and expressed in terms of polystyrene.

In the actinic ray-sensitive or radiation-sensitive resin composition,the content of the resin represented by Formula (I) based on the totalsolid content of the actinic ray-sensitive or radiation-sensitive resincomposition is preferably 30% to 99% by mass in general, and morepreferably 50% to 95% by mass.

(Repeating Unit Having Phenolic Hydroxyl Group)

The resin P may contain a repeating unit having a phenolic hydroxylgroup.

Examples of the repeating unit having a phenolic hydroxyl group includea repeating unit represented by General Formula (I).

In the formula, R₄₁, R₄₂, and R₄₃ each independently represent ahydrogen atom, an alkyl group, a halogen atom, a cyano group, or analkoxycarbonyl group. Here, R₄₂ and Ar₄ may form a ring by being bondedto each other. In this case, R₄₂ represents a single bond or an alkylenegroup.

X₄ represents a single bond, —COO—, or —CONR₆₄—, and R₆₄ represents ahydrogen atom or an alkyl group.

L₄ represents a single bond or an alkylene group.

Ar₄ represents an (n+1)-valent aromatic ring group. In a case where Ar₄forms a ring by being bonded to R₄₂, Ar₄ represents an (n+2)-valentaromatic ring group.

n represents an integer of 1 to 5.

The alkyl group represented by R₄₁, R₄₂, and R₄₃ in General Formula (I)is preferably an alkyl group having 20 or less carbon atoms such as amethyl group, an ethyl group, a propyl group, an isopropyl group, an-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group,an octyl group, or a dodecyl group which may have a substituent, morepreferably an alkyl group having 8 or less carbon atoms, and even morepreferably an alkyl group having 3 or less carbon atoms.

The cycloalkyl group represented by R₄₁, R₄₂, and R₄₃ in General Formula(I) may be monocyclic or polycyclic. The cycloalkyl group is preferablya monocyclic cycloalkyl group having 3 to 8 carbon atoms such as acyclopropyl group, a cyclopentyl group, or a cyclohexyl group which mayhave a substituent.

Examples of the halogen atom represented by R₄₁, R₄₂, and R₄₃ in GeneralFormula (I) include a fluorine atom, a chlorine atom, a bromine atom,and an iodine atom. Among these, a fluorine atom is preferable.

As the alkyl group contained in the alkoxycarbonyl group represented byR₄₁, R₄₂, and R₄₃ in General Formula (I), the same alkyl group as thealkyl group represented by R₄₁, R₄₂, and R₄₃ described above ispreferable.

Examples of the substituent in each of the above groups include an alkylgroup, a cycloalkyl group, an aryl group, an amino group, an amidegroup, a ureide group, a urethane group, a hydroxyl group, a carboxylgroup, a halogen atom, an alkoxy group, a thioether group, an acylgroup, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitrogroup, and the like. The number of carbon atoms in the substituent ispreferably equal to or smaller than 8.

Ar₄ represents an (n+1)-valent aromatic ring group. Examples of adivalent aromatic ring group obtained in a case where n is 1 include anarylene group having 6 to 18 carbon atoms such as a phenylene group, atolylene group, a naphthylene group, or an anthracenylene group whichmay have a substituent and an aromatic ring group containing a heteroring such as thiophene, furan, pyrrole, benzothiophene, benzofuran,benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole,or thiazole.

Specific examples of the (n+1)-valent aromatic ring group obtained in acase where n is an integer equal to or greater than 2 include groupsobtained by removing (n−1) pieces of any hydrogen atoms from thespecific examples of the divalent aromatic ring group described above.

The (n+1)-valent aromatic ring group may further have a substituent.

Examples of the substituent that the alkyl group, the cycloalkyl group,the alkoxycarbonyl group, the alkylene group, and the (n+1)-valentaromatic ring group described above can include the alkyl groupexemplified as R₄₁, R₄₂, and R₄₃ in General Formula (I); an alkoxy groupsuch as a methoxy group, an ethoxy group, a hydroxyethoxy group, apropoxy group, a hydroxypropoxy group, or a butoxy group; and an arylgroup such as a phenyl group.

Examples of the alkyl group represented by R₆₄ in —CONR₆₄— (R₆₄represents a hydrogen atom or an alkyl group) represented by X₄ includean alkyl group having 20 or less carbon atoms such as a methyl group, anethyl group, a propyl group, an isopropyl group, a n-butyl group, asec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, ora dodecyl group which may have a substituent. Among these, an alkylgroup having 8 or less carbon atoms is more preferable.

X₄ is preferably a single bond, —COO—, or —CONH—, and more preferably asingle bond or —COO—.

The alkylene group represented by L₄ is preferably an alkylene grouphaving 1 to 8 carbon atoms such as a methylene group, an ethylene group,a propylene group, a butylene group, a hexylene group, or an octylenegroup which may have a substituent.

Ar₄ is preferably an aromatic ring group having 6 to 18 carbon atomsthat may have a substituent, and more preferably a benzene ring group, anaphthalene ring group, or a biphenylene ring group.

It is preferable that the repeating unit represented by General Formula(I) comprises a hydroxystyrene structure. That is, Ar₄ is preferably abenzene ring group.

The repeating unit having a phenolic hydroxyl group is preferably arepeating unit represented by General Formula (p1).

R in General Formula (p1) represents a hydrogen atom, a halogen atom, ora linear or branched alkyl group having 1 to 4 carbon atoms. A pluralityof R's may be the same as or different from each other. As R in GeneralFormula (p1), a hydrogen atom is preferable.

Ar in General Formula (p1) represents an aromatic ring, and examplesthereof include an aromatic hydrocarbon ring having 6 to 18 carbon atomsthat may have a substituent, such as a benzene ring, a naphthalene ring,an anthracene ring, a fluorene ring, or a phenanthrene ring, and anaromatic hetero ring containing a hetero ring such as a thiophene ring,a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring,a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazolering, a triazole ring, a thiadiazole ring, or a thiazole ring. Amongthese, a benzene ring is more preferable.

m in General Formula (p1) represents an integer of 1 to 5. m ispreferably 1.

Specific examples of the repeating unit having a phenolic hydroxyl groupwill be shown below, but the present invention is not limited thereto.In the formulae, a represents 1 or 2.

The content of the repeating unit having a phenolic hydroxyl group withrespect to all the repeating units in the resin P is preferably 0 to 50mol %, more preferably 0 to 45 mol %, and even more preferably 0 to 40mol %.

(Repeating Unit Containing Organic Group Having Polar Group)

The resin P may further contain a repeating unit containing an organicgroup having a polar group, particularly, a repeating unit having analicyclic hydrocarbon structure substituted with a polar group.

In a case where the resin P further contains such a repeating unit, thesubstrate adhesiveness and the affinity with a developer are improved.As the alicyclic hydrocarbon structure substituted with a polar group,an adamantyl group, a diamantyl group, or a norbornane group ispreferable. As the polar group, a hydroxyl group or a cyano group ispreferable.

Specific examples of the repeating unit having a polar group will beshown below, but the present invention is not limited thereto.

In a case where the resin P contains the repeating unit containing anorganic group having a polar group, the content of the repeating unitwith respect to all the repeating units in the resin P is preferably 1to 50 mol %, more preferably 1 to 30 mol %, even more preferably 5 to 25mol %, and particularly preferably 5 to 20 mol %.

(Repeating Unit Having Group (Photoacid Generating Group) GeneratingAcid by Irradiation of Actinic Rays or Radiation)

The resin P may contain a repeating unit having a group (photoacidgenerating group) generating an acid by the irradiation of actinic raysor radiation.

Examples of the repeating unit having a group (photoacid generatinggroup) generating an acid by the irradiation of actinic rays orradiation include a repeating unit represented by Formula (4).

R⁴¹ represents a hydrogen atom or a methyl group. L⁴¹ represents asingle bond or a divalent linking group. L⁴² represents a divalentlinking group. W represents a structural moiety generating an acid on aside chain by being decomposed by the irradiation of actinic rays orradiation.

Specific examples of the repeating unit represented by Formula (4) willbe shown below, but the present invention is not limited thereto.

Examples of the repeating unit represented by Formula (4) also includethe repeating units described in paragraphs [0094] to [0105] inJP2014-041327A.

In a case where the resin P contains the repeating unit having aphotoacid generating group, the content of the repeating unit having aphotoacid generating group with respect to all the repeating units inthe resin P is preferably 1 to 40 mol %, more preferably 5 to 35 mol %,and even more preferably 5 to 30 mol %.

The resin P may contain a repeating unit represented by Formula (VI).

In Formula (VI), R₆₁, R₆₂, and R₆₃ each independently represent ahydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, acyano group, or an alkoxycarbonyl group. Here, R₆₂ may form a ring bybeing bonded to Ar₆, and in this case, R₆₂ represents a single bond oran alkylene group.

X₆ represents a single bond, —COO—, or —CONR₆₄—. R₆₄ represents ahydrogen atom or an alkyl group.

L₆ represents a single bond or an alkylene group.

Ar₆ represents an (n+1)-valent aromatic ring group. In a case where Ar₆forms a ring by being bonded to R₆₂, Ar₆ represents an (n+2)-valentaromatic ring group.

In a case where n≥2, Y₂ each independently represents a hydrogen atom ora group which is dissociated by the action of an acid. Here, at leastone of Y₂'s represents a group which is dissociated by the action of anacid.

n represents an integer of 1 to 4.

As the group Y₂ which is dissociated by the action of an acid, astructure represented by Formula (VI-A) is preferable.

L₁ and L₂ each independently represent a hydrogen atom, an alkyl group,a cycloalkyl group, an aryl group, or a group obtained by combining analkylene group and an aryl group.

M represents a single bond or a divalent linking group.

Q represents an alkyl group, a cycloalkyl group which may contain aheteroatom, an aryl group which may contain a heteroatom, an aminogroup, an ammonium group, a mercapto group, a cyano group, or analdehyde group.

At least two out of Q, M, and L₁ may form a ring (preferably a 5- or6-membered ring) by being bonded to each other.

The repeating unit represented by Formula (VI) is preferably a repeatingunit represented by Formula (3).

In Formula (3), Ar₃ represents an aromatic ring group.

R₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, anaryl group, an aralkyl group, an alkoxy group, an acyl group, or aheterocyclic group.

M₃ represents a single bond or a divalent linking group.

Q₃ represents an alkyl group, a cycloalkyl group, an aryl group, or aheterocyclic group.

At least two out of Q₃, M₃, and R₃ may form a ring by being bonded toeach other.

The aromatic ring group represented by Ar₃ is the same as Ar₆ in Formula(VI) in a case where n in Formula (VI) is 1. Ar₃ is more preferably aphenylene group or a naphthylene group, and even more preferably aphenylene group.

Specific examples of the repeating unit represented by Formula (VI) willbe shown below, but the present invention is not limited thereto.

The resin P may contain a repeating unit represented by Formula (4).

In Formula (4), R₄₁, R₄₂, and R₄₃ each independently represent ahydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, acyano group, or an alkoxycarbonyl group. R₄₂ and L₄ may form a ring bybeing bonded to each other, and in this case, R₄₂ represents an alkylenegroup.

L₄ represents a single bond or a divalent linking group. In a case whereL₄ forms a ring together with R₄₂, L₄ represents a trivalent linkinggroup.

R₄₄ and R₄₅ each represent a hydrogen atom, an alkyl group, a cycloalkylgroup, an aryl group, an aralkyl group, an alkoxy group, an acyl group,or a heterocyclic group.

M₄ represents a single bond or a divalent linking group.

Q₄ represents an alkyl group, a cycloalkyl group, an aryl group, or aheterocyclic group.

At least two out of Q₄, M₄, and R₄₄ may form a ring by being bonded toeach other.

R₄₁, R₄₂, and R₄₃ have the same definition as R₄₁, R₄₂, and R₄₃ inFormula (IA), and the preferable range thereof is also the same.

L₄ has the same definition as T in Formula (AI), and the preferablerange thereof is also the same.

R₄₄ and R₄₅ have the same definition as R₃ in Formula (3), and thepreferable range thereof is also the same.

M₄ has the same definition as M₃ in Formula (3), and the preferablerange thereof is also the same.

Q₄ has the same definition as Q₃ in Formula (3), and the preferablerange thereof is also the same.

Examples of the ring formed by bonding of at least two out of Q₄, M₄,and R₄₄ include a ring formed by bonding of at least two out of Q₃, M₃,and R₃, and the preferable range thereof is also the same.

Specific examples of the repeating unit represented by Formula (4) willbe shown below, but the present invention is not limited thereto.

The resin P may contain a repeating unit represented by Formula (BZ).

In Formula (BZ), AR represents an aryl group. Rn represents an alkylgroup, a cycloalkyl group, or an aryl group. Rn and AR may form anonaromatic ring by being bonded to each other.

R₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, ahalogen atom, a cyano group, or an alkyloxycarbonyl group.

Specific examples of the repeating unit represented by Formula (BZ) willbe shown below, but the present invention is not limited thereto.

In the resin P, the content of the repeating unit having anacid-decomposable group (total content in a case where the resin Pcontains a plurality of kinds of the repeating units) with respect toall the repeating units in the resin P is preferably 5 to 80 mol %, morepreferably 5 to 75 mol %, and even more preferably 10 to 65 mol %.

The resin P may contain a repeating unit represented by Formula (V) orFormula (VI).

In the formulae, R₆ and R₇ each independently represent a hydrogen atom,a hydroxy group, a linear, branched, and cyclic alkyl group having 1 to10 carbon atoms, an alkoxy group, an acyloxy group, a cyano group, anitro group, an amino group, a halogen atom, an ester group (—OCOR or—COOR: R represents an alkyl group having 1 to 6 carbon atoms or afluorinated alkyl group), or a carboxyl group.

n₃ represents an integer of 0 to 6.

n₄ represents an integer of 0 to 4.

X₄ represents a methylene group, an oxygen atom, or a sulfur atom.

Specific examples of the repeating unit represented by Formula (V) orFormula (VI) will be shown below, but the present invention is notlimited thereto.

The resin P may further contain a repeating unit having a silicon atomon a side chain. Examples of the repeating unit having a silicon atom ona side chain include a (meth)acrylic repeating unit having a siliconatom, a vinyl-based repeating unit having a silicon atom, and the like.Typically, the repeating unit having a silicon atom on a side chain is arepeating unit having a group having a silicon atom on a side chain.Examples of the group having a silicon atom include a trimethylsilylgroup, a triethylsilyl group, a triphenylsilyl group, atricyclohexylsilyl group, a tristrimethylsiloxysilyl group, atristrimethylsilyl silyl group, a methyl bistrimethylsilyl silyl group,a methyl bistrimethylsiloxysilyl group, a dimethyltrimethylsilyl silylgroup, a dimethyl trimethylsiloxysilyl group, cyclic or linearpolysiloxane shown below, a cage-like, ladder-like, or randomsilsesquioxane structure, and the like. In the formulae, R and R¹ eachindependently represent a monovalent substituent. * represents a bond.

As the repeating unit having the aforementioned group, for example, arepeating unit derived from an acrylate or methacrylate compound havingthe aforementioned group or a repeating unit derived from a compoundhaving the aforementioned group and a vinyl group is preferable.

It is preferable that the repeating unit having a silicon atom ispreferably a repeating unit having a silsesquioxane structure. In a casewhere the repeating unit has a silsesquioxane structure, in forming anultrafine pattern (for example, a line width equal to or smaller than 50nm) having a cross-sectional shape with a high aspect ratio (forexample, film thickness/line width is equal to or greater than 3), anextremely excellent collapse performance can be demonstrated.

Examples of the silsesquioxane structure include a cage-likesilsesquioxane structure, a ladder-like silsesquioxane structure, and arandom silsesquioxane structure. Among these, a cage-like silsesquioxanestructure is preferable.

The cage-like silsesquioxane structure is a silsesquioxane structurehaving a cage-like skeleton. The cage-like silsesquioxane structure maybe a complete cage-like silsesquioxane structure or an incompletecage-like silsesquioxane structure, but is preferably a completecage-like silsesquioxane structure.

The ladder-like silsesquioxane structure is a silsesquioxane structurehaving a ladder-like skeleton.

The random silsesquioxane structure is a silsesquioxane structure havinga random skeleton.

The cage-like silsesquioxane structure is preferably a siloxanestructure represented by Formula (S).

In Formula (S), R represents a monovalent organic group. A plurality ofR's may be the same as or different from each other.

The organic group is not particularly limited, and specific examplesthereof include a hydroxy group, a nitro group, a carboxy group, analkoxy group, an amino group, a mercapto group, a blocked mercapto group(for example, a mercapto group blocked (protected) by an acyl group), anacyl group, an imide group, a phosphino group, a phosphinyl group, asilyl group, a vinyl group, a hydrocarbon group which may have aheteroatom, a (meth)acryl group-containing group, an epoxygroup-containing group, and the like.

Examples of the heteroatom in the hydrocarbon group which may have aheteroatom include an oxygen atom, a nitrogen atom, a sulfur atom, aphosphorus atom, and the like.

Examples of the hydrocarbon group which may have a heteroatom include analiphatic hydrocarbon group, an aromatic hydrocarbon group, a groupobtained by combining these, and the like.

The aliphatic hydrocarbon group may be any of a linear, branched, orcyclic aliphatic hydrocarbon group. Specific examples of the aliphatichydrocarbon group include a linear or branched alkyl group (particularlyhaving 1 to 30 carbon atoms), a linear or branched alkenyl group(particularly having 2 to 30 carbon atoms), a linear or branched alkynylgroup (particularly having 2 to 30 carbon atoms), and the like.

Examples of the aromatic hydrocarbon group include an aromatichydrocarbon group having 6 to 18 carbon atoms such as a phenyl group, atolyl group, a xylyl group, or a naphthyl group.

In a case where the resin P has the repeating unit having a silicon atomon a side chain, the content of the repeating unit with respect to allthe repeating units in the resin P is preferably 1 to 30 mol %, morepreferably 5 to 25 mol %, and even more preferably 5 to 20 mol %.

The weight-average molecular weight of the resin P that is measured by aGel permeation chromatography (GPC) method and expressed in terms ofpolystyrene is preferably 1,000 to 200,000, more preferably 3,000 to20,000, and even more preferably 5,000 to 15,000. In a case where theweight-average molecular weight is 1,000 to 200,000, it is possible toprevent the deterioration of heat resistance and dry etching resistance,to prevent the deterioration of developability, and to prevent filmforming properties from deteriorating due to the increase in viscosity.

The dispersity (molecular weight distribution) is generally 1 to 5,preferably 1 to 3, more preferably 1.2 to 3.0, and even more preferably1.2 to 2.0.

In the actinic ray-sensitive or radiation-sensitive resin composition,the content of the resin P in the total solid content is preferably 50%to 99.9% by mass, and more preferably 60% to 99.0% by mass.

In the actinic ray-sensitive or radiation-sensitive resin composition,one kind of resin P may be used, or a plurality of resins P may be usedin combination.

(Photoacid Generator)

It is preferable that the actinic ray-sensitive or radiation-sensitiveresin composition contains a photoacid generator. As the photoacidgenerator, known photoacid generators can be used without particularlimitation.

The content of the photoacid generator in the actinic ray-sensitive orradiation-sensitive resin composition is not particularly limited.However, generally, the content of the photoacid generator with respectto the total solid content of the actinic ray-sensitive orradiation-sensitive resin composition is preferably 0.1% to 20% by mass,and more preferably 0.5% to 20% by mass. One kind of photoacid generatormay be used singly, or two or more kinds of photoacid generators may beused in combination. In a case where two or more kinds of photoacidgenerators are used in combination, the total content thereof ispreferably within the above range.

Examples of the photoacid generator include the compounds described inJP2016-057614A, JP2014-219664A, JP2016-138219A, and JP2015-135379A.

(Quencher)

The actinic ray-sensitive or radiation-sensitive resin composition maycontain a quencher. As the quencher, known quenchers can be used withoutparticular limitation.

The quencher is a basic compound and has a function of inhibiting theacid-decomposable resin from being unintentionally decomposed in anunexposed area by the acid spread from an exposed area.

The content of the quencher in the actinic ray-sensitive orradiation-sensitive resin composition is not particularly limited.However, generally, the content of the quencher with respect to thetotal solid content of the actinic ray-sensitive or radiation-sensitiveresin composition is preferably 0.1% to 15% by mass, and more preferably0.5% to 8% by mass. One kind of quencher may be used singly, or two ormore kinds of quenchers may be used in combination. In a case where twoor more kinds of quenchers are used in combination, the total contentthereof is preferably within the above range.

Examples of the quencher include the compounds described inJP2016-057614A, JP2014-219664A, JP2016-138219A, and JP2015-135379A.

(Hydrophobic Resin)

The actinic ray-sensitive or radiation-sensitive resin composition maycontain a hydrophobic resin.

It is preferable to design the hydrophobic resin such that the resin islocalized within the surface of a resist film. However, unlike asurfactant, the hydrophobic resin does not need to have a hydrophilicgroup in a molecule and may not make a contribution to the homogeneousmixing of a polar substance with a nonpolar substance.

The addition of the hydrophobic resin brings about effects such as thecontrol of static and dynamic contact angle formed between water and theresist film surface and the inhibition of outgas.

From the viewpoint of localization within the surface layer of a film,the hydrophobic resin preferably has any one or more kinds of groupsamong “fluorine atom”, “silicon atom”, and “CH₃ partial structureincluded in a side chain portion of the resin”, and more preferably hastwo or more kinds of groups among the above. Furthermore, it ispreferable that the hydrophobic resin has a hydrocarbon group having 5or more carbon atoms. These groups may be positioned in the main chainof the resin or may substitute a side chain of the resin.

In a case where the hydrophobic resin contains a fluorine atom and/or asilicon atom, the fluorine atom and/or the silicon atom in thehydrophobic resin may be contained in the main chain or the side chainof the resin.

In a case where the hydrophobic resin contains a fluorine atom, as apartial structure having the fluorine atom, a fluorine atom-containingalkyl group, a fluorine atom-containing cycloalkyl group, or a fluorineatom-containing aryl group is preferable.

The fluorine atom-containing alkyl group (preferably having 1 to 10carbon atoms and more preferably having 1 to 4 carbon atoms) is a linearor branched alkyl group in which at least one hydrogen atom issubstituted with a fluorine atom and which may further have asubstituent other than a fluorine atom.

The fluorine atom-containing cycloalkyl group is a monocyclic orpolycyclic cycloalkyl group in which at least one hydrogen atom issubstituted with a fluorine atom and which may further have asubstituent other than a fluorine atom.

Examples of the fluorine atom-containing aryl group include an arylgroup in which at least one hydrogen atom is substituted with a fluorineatom, such as a phenyl group or a naphthyl group. The fluorineatom-containing aryl group may further have a substituent other than afluorine atom.

Examples of the repeating unit having a fluorine atom or a silicon atominclude the repeating units exemplified in paragraph [0519] inUS2012/0251948A1.

As described above, it is also preferable that the hydrophobic resincontains a CH₃ partial structure in a side chain portion.

Herein, the CH₃ partial structure that the side chain portion of thehydrophobic resin has includes a CH₃ partial structure that an ethylgroup, a propyl group, or the like has.

A methyl group directly bonded to the main chain of the hydrophobicresin (for example, an α-methyl group of a repeating unit having amethacrylic acid structure) makes a small contribution to the surfacelocalization of the hydrophobic resin due to the influence of the mainchain. Accordingly, such a methyl group is not included in the CH₃partial structure in the present invention.

Regarding the hydrophobic resin, the description in paragraphs [0348] to[0415] in JP2014-010245A can be referred to, and the entire contentsthereof are incorporated into the present specification.

As the hydrophobic resin, in addition to the above resins, the resinsdescribed in JP2011-248019A, JP2010-175859A, and JP2012-032544A can alsobe preferably used.

As the hydrophobic resin, for example, resins represented by Formula(1b) to Formula (5b) are preferable.

In a case where the resist composition contains the hydrophobic resin,the content of the hydrophobic resin with respect to the total solidcontent of the composition is preferably 0.01% to 20% by mass, and morepreferably 0.1% to 15% by mass.

(Solvent)

The actinic ray-sensitive or radiation-sensitive resin composition maycontain a solvent. As the solvent, known solvents can be used withoutparticular limitation.

The solvent to be incorporated into the actinic ray-sensitive orradiation-sensitive resin composition may be the same as or differentfrom the organic solvent to be incorporated into the mixture in thechemical liquid described above.

The content of the solvent in the actinic ray-sensitive orradiation-sensitive resin composition is not particularly limited.However, generally, it is preferable that the solvent is incorporatedinto the composition such that the total solid content of the actinicray-sensitive or radiation-sensitive resin composition is adjusted to be0.1% to 20% by mass. One kind of solvent may be used singly, or two ormore kinds of solvents may be used in combination. In a case where twoor more kinds of solvents are used in combination, the total contentthereof is preferably within the above range.

Examples of the solvent include the solvents described inJP2016-057614A, JP2014-219664A, JP2016-138219A, and JP2015-135379A.

(Other Additives)

If necessary, the actinic ray-sensitive or radiation-sensitive resincomposition may additionally contain a surfactant, an acid proliferationagent, a dye, a plasticizer, a photosensitizer, a light absorber, analkali-soluble resin other than the above resins, and/or a dissolutioninhibitor.

[(C) Exposure Step]

The exposure step is a step of exposing the resist film. As the methodfor exposing the resist film, known methods can be used withoutparticular limitation.

Examples of the method for exposing the resist film include a method ofirradiating the resist film with actinic rays or radiation through apredetermined mask. In a case where the method of irradiating the resistfilm with electron beams is used, the resist film may be irradiatedwithout the intervention of a mask (this is referred to as “directimaging” as well in some cases).

The actinic rays or the radiation used for exposure is not particularlylimited, and examples thereof include a KrF excimer laser, an ArFexcimer laser, Extreme Ultra Violet (EUV), Electron Beam (EB), and thelike. Among these, EUV or EB is preferable. The exposure may beimmersion exposure.

<Post Exposure Bake (PEB) Step>

It is preferable that the aforementioned pattern forming methodadditionally includes a Post Exposure Bake (PEB) step of baking theexposed resist film between the exposure step and the development step.By the baking, the reaction in the exposed portion is accelerated, andeither or both of sensitivity and pattern shape are further improved.

The heating temperature is preferably 80° C. to 150° C., more preferably80° C. to 140° C., and even more preferably 80° C. to 130° C.

The heating time is preferably 30 to 1,000 seconds, more preferably 60to 800 seconds, and even more preferably 60 to 600 seconds.

The heating can be performed by means comprising a generalexposure⋅development machine, or may be performed using a hot plate orthe like.

[(D) Development Step]

The development step is a step of developing the exposed resist film(hereinafter, referred to as “resist film obtained after exposure” aswell) by using a developer.

As the development method, known development methods can be used withoutparticular limitation. Examples of the development method includedipping method, a puddle method, a spray method, a dynamic dispensemethod, and the like.

Furthermore, the aforementioned pattern forming method may additionallyinclude a step of substituting the developer with another solvent so asto stop the development after the development step.

The development time is not particularly limited, but is preferably 10to 300 seconds in general and more preferably 10 to 120 seconds. Thetemperature of the developer is preferably 0° C. to 50° C., and morepreferably 15° C. to 35° C. In the pattern forming method, thedevelopment step may be performed at least once or plural times.

<Developer>

As the developer, known developers can be used without particularlimitation. Examples of the developer include an alkaline developer anda developer containing an organic solvent (organic developer).

In the development step, both the development using a developercontaining an organic solvent and development using an alkalinedeveloper may be performed (so-called double development may beperformed).

<Rinsing Step>

It is preferable that the aforementioned pattern forming methodadditionally includes a rinsing step after the development step.

The rinsing step is a step of washing the wafer, which comprises theresist film obtained after development, by using a rinsing solution.

As the washing method, known washing methods can be used withoutparticular limitation. Examples thereof include a rotation jettingmethod, a dipping method, a spray method, and the like.

Among these, it is preferable to use the rotation jetting method inwhich the wafer is washed and then rotated at a rotation speed of 2,000to 4,000 rpm such that the rinsing solution is removed from thesubstrate.

The rinsing time is preferably 10 to 300 seconds in general, morepreferably 10 to 180 seconds, and even more preferably 20 to 120seconds. The temperature of the rinsing solution is preferably 0° C. to50° C., and more preferably 15° C. to 35° C.

(Rinsing Solution)

In a case where the wafer comprising the resist film is rinsed after thedevelopment using an alkaline developer, as the rinsing solution, purewater is preferable. The rinsing solution may be pure water containing asurfactant.

In a case where the wafer comprising the resist film is rinsed after thedevelopment using an organic developer, as the rinsing solution, arinsing solution containing an organic solvent is preferable. As theorganic solvent contained in the rinsing solution, for example, at leastone kind of organic solvent selected from the group consisting of ahydrocarbon-based solvent, a ketone-based solvent, an ester-basedsolvent, an alcohol-based solvent, an amide-based solvent, and anether-based solvent is preferable, at least one kind of organic solventselected from the group consisting of a hydrocarbon-based solvent, anether-based solvent, and a ketone-based solvent is more preferable, andat least one kind of organic solvent selected from the group consistingof a hydrocarbon-based solvent and an ether-based solvent is even morepreferable.

In a case where the developer containing an organic solvent is used inthe development step, the aforementioned pattern forming method mayinclude the rinsing step after the development step. However, from theviewpoint of throughput (productivity), the pattern forming method maynot include the rinsing step.

As the pattern forming method that does not include a rinsing step, forexample, the description in paragraphs [0014] to [0086] inJP2015-216403A can be cited, and the contents thereof are incorporatedinto the present specification.

As the rinsing solution, methyl isobutyl carbinol (MIBC) or the sameliquid (particularly, butyl acetate) as the developer is alsopreferable.

<Other Steps>

The aforementioned pattern forming method may include other steps inaddition to the steps described above. Examples of those other stepsinclude a washing step using a supercritical fluid, a heating step, andthe like.

(Removing Step Using Supercritical Fluid)

A removing step using a supercritical fluid is a step of removing thedeveloper and/or the rinsing solution having adhered to the patternsurface by using a supercritical fluid after the development treatmentand/or the rinsing treatment.

(Heating Step)

The heating step is a step of heating the resist film so as to removethe solvent remaining in the pattern after the development step, therinsing step, or the removing step using a supercritical fluid.

The heating temperature is not particularly limited, but is preferably40° C. to 160° C. in general, more preferably 50° C. to 150° C., andeven more preferably 50° C. to 110° C.

The heating time is not particularly limited, but is preferably 15 to300 seconds in general and more preferably 15 to 180 seconds.

[Kit]

The kit according to an embodiment of the present invention is a kitcomprising the chemical liquid and an actinic ray-sensitive orradiation-sensitive resin composition.

The kit according to an embodiment of the present invention is a kithaving the chemical liquid described above and an actinic ray-sensitiveor radiation-sensitive resin composition. The aspect of the kit is notparticularly limited, and examples thereof include an aspect having achemical liquid storage body which has a first container and a chemicalliquid stored in the first container and an actinic ray-sensitive orradiation-sensitive resin composition storage body which has a secondcontainer and an actinic ray-sensitive or radiation-sensitive resincomposition stored in the second container. The chemical liquid and theactinic ray-sensitive or radiation-sensitive resin composition are asdescribed above. Furthermore, as the first container and the secondcontainer, those described above as containers of the chemical liquidstorage body can be used.

In the kit, the chemical liquid can be used as a prewet solution, awashing solution including the aspect of a rinsing solution, adeveloper, or the like. It is preferable that the chemical liquid isused as a prewet solution. That is, the chemical liquid in the kit canbe used as a prewet solution, and the kit can be used for forming aresist film on a substrate, which has been pre-wetted by the chemicalliquid, by the method described above by using the actinic ray-sensitiveor radiation-sensitive resin composition in the kit. In a case where thekit is used, the occurrence of a defect is further inhibited.

The kit according to another embodiment of the present invention is akit comprising the chemical liquid and an actinic ray-sensitive orradiation-sensitive resin composition containing a resin having a groupgenerating a polar group by being decomposed by the action of an acid.The kit satisfies the following conditions 1 and 2.

Condition 1: Rsq1 calculated by Equation 1 based on a proton spin-spinrelaxation time measured at 25° C. for a chemical liquid and a firsttest solution formed of a resin and the chemical liquid by using apulsed nuclear magnetic resonance-type particle interface characteristicevaluator is higher than 0.5.

Rsq1=(τ0/τ1)−1  (Equation 1)

In Equation 1, τ0 represents the spin-spin relaxation time of thechemical liquid, and τ1 represents the spin-spin relaxation time of thefirst test solution.

Condition 2: SRsq calculated by Equation 2 based on the proton spin-spinrelaxation time measured at 25° C. for a second test solution, which isformed of the resin and the chemical liquid and in which the content ofthe resin is different from the content of the resin in the first testsolution, and the first test solution by using a pulsed nuclear magneticresonance-type particle interface characteristic evaluator is higherthan −1.

SRsq=(Rsq2−Rsq1)/(c2−c1)  (Equation 2)

In Equation 2, Rsq1 represents a value calculated by Equation 1, andRsq2 represents a value calculated by Equation 3. c1 and c2 represent amass-based content of the resin in the first test solution and thesecond test solution respectively. The unit of the mass-based content is% by mass, and c2>c1.

Rsq2=(τ0/τ2)−1  (Equation 3)

In Equation 3, TO has the same definition as τ0 in Equation 1, and τ2represents a spin-spin relaxation time of the second test solution.

The above testing method is the same as what is explained in “Affinitybetween chemical liquid and resin” in the description of the patternforming method. In the kit according to the above embodiment, thechemical liquid and the resin exhibit further improved affinity.Therefore, in a case where the chemical liquid in the kit is used as aprewet solution, and a resist film is formed on a substrate, which hasbeen pre-wetted by the chemical liquid, by using the actinicray-sensitive or radiation-sensitive resin composition, the occurrenceof a defect resulting from solvent shock or the like is furtherinhibited.

Examples

Hereinafter, the present invention will be more specifically describedbased on examples. The materials, the amount and proportion of thematerials used, the details of treatments, the procedure of treatments,and the like shown in the following examples can be appropriatelymodified as long as the gist of the present invention is maintained.Accordingly, the scope of the present invention is not limited to thefollowing examples.

[Preparation of Organic Solvent]

In order to manufacture chemical liquids of examples and comparativeexamples, the following organic solvents were prepared. As each of theorganic solvents, a high-purity grade with purity equal to or higherthan 99% by mass was used. The abbreviation for each organic solvent isshown in the bracket.

-   -   Propylene glycol monomethyl ether (PGME)    -   Cyclopentanone (CyPn)    -   Butyl acetate (nBA)    -   Propylene glycol monomethyl ether acetate (PGMEA)    -   Cyclohexanone (CyHx)    -   Ethyl lactate (EL)    -   2-Hydroxymethyl isobutyrate (HBM)    -   Cyclopentanone dimethyl acetal (DBCPN)    -   Propylene carbonate (PC)    -   γ-Butyrolactone (GBL)    -   Dimethyl sulfoxide (DMSO)    -   Ethylene carbonate (EC)    -   1-Methyl-2-pyrrolidone (NMP)    -   3-Methoxymethyl propionate (MMP)    -   Ethylene glycol monomethyl ether acetate (EGMEA)    -   3-Ethoxyethyl propionate (EEP)    -   Anisole

[Preparation of Chemical Liquid]

Organic solvents of the types described in Table 1 were mixed togetherat the mass ratio described in Table 1, thereby obtaining a mixture. Theobtained mixture was purified, thereby preparing a chemical liquid.

[Measurement of Content of Each Component Contained in Chemical Liquid,and the Like]

For measuring the content of each component contained in the chemicalliquid, the following method was used. All of the following measurementswere performed in a clean room that met the level equal to or lower thanInternational Organization for Standardization (ISO) Class 2. In orderto improve the measurement accuracy, at the time of measuring eachcomponent, in a case where the content of the component was found to beequal to or smaller than a detection limit by general measurement, theorganic solvent was concentrated by 1/100 in terms of volume forperforming the measurement, and the content was calculated by convertingthe concentration into the content of the organic solvent not yet beingconcentrated. The results are summarized in Table 1.

<Organic Solvent>

The content of the organic solvent and the organic impurity in each ofthe chemical liquids was measured using a gas chromatography massspectrometry (tradename “GCMS-2020”, manufactured by ShimadzuCorporation, the measurement conditions were as described below).

(Measurement Condition)

Capillary column: InertCap 5MS/NP 0.25 mmI.D.×30 m df=0.25 μm

Sample introduction method: slit 75 kPa constant pressure

Vaporizing chamber temperature: 230° C.

Column oven temperature: 80° C. (2 min)-500° C. (13 min) heating rate15° C./min

Carrier gas: helium

Septum purge flow rate: 5 mL/min

Split ratio: 25:1

Interface temperature: 250° C.

Ion source temperature: 200° C.

Measurement mode: Scan m/z=85˜500

Amount of sample introduced: 1

[Physical Properties of Chemical Liquid or Mixture]

The physical properties of each of the chemical liquids or the mixtureswere measured or calculated by the following method.

<Surface Tension>

Based on a surface tension at 25° C. of each of the organic solventscontained in the mixture and a molar fraction of each of the organicsolvents in the mixture, the surface tension of the mixture wascalculated. The calculated values are shown in Table 1.

The surface tension at 25° C. of the organic solvents contained in eachof the mixtures was measured using a surface tensiometer (trade name“CBVP-Z” manufactured by Kyowa Interface Science Co., LTD.).

<Hansen Solubility Parameter>

The hydrogen bond element and the dispersion element as Hansensolubility parameters of each of the organic solvents were calculatedusing Hansen Solubility Parameters in Practice (HSPiP). The calculatedvalues are shown in Table 1.

<Vapor Pressure>

The vapor pressure of the mixture of the organic solvents was calculatedby summing up the product of a vapor pressure (Pa) of each of theorganic solvents at 25° C. and the molar fraction of each of the organicsolvents in the mixture. The calculated values are shown in Table 1.

[Preparation of Actinic Ray-Sensitive or Radiation-Sensitive ResinComposition]

By the following method, actinic ray-sensitive or radiation-sensitiveresin (resist) compositions were prepared. By mixing together componentsand then filtering the mixture through a polyethylene filter having apore size of 0.03 μm, the resist compositions were prepared.Hereinafter, each of the actinic ray-sensitive or radiation-sensitiveresin compositions 1 to 6 will be described.

<Resist Composition 1>

Acid-decomposable resin (resin represented by the following formula(weight-average molecular weight (Mw): 7,500): the numerical valuedescribed for each repeating unit means mol %): 100 parts by mass

Photoacid generator shown below: 8 parts by mass

Quenchers shown below: 5 parts by mass (the mass ratio is0.1:0.3:0.3:0.2 from left to right).

Among the following quenchers, a polymer-type quencher has aweight-average molecular weight (Mw) of 5,000. The numerical valuedescribed for each repeating unit means molar ratio.

Hydrophobic resins shown below: 4 parts by mass (the mass ratio is0.5:0.5 from left to right).

Between the following hydrophobic resins, the hydrophobic resin on theleft side has a weight-average molecular weight (Mw) of 7,000, and thehydrophobic resin on the right side has a weight-average molecularweight (Mw) of 8,000. In each of the hydrophobic resins, the numericalvalue described for each repeating unit means molar ratio.

Solvent:

Propylene glycol monomethyl ether acetate (PGMEA): 3 parts by mass

Cyclohexanone: 600 parts by mass

γ-Butyrolactone (γ-BL): 100 parts by mass

<Resist Composition 2>

Acid-decomposable resin (resin represented by the following formula(weight-average molecular weight (Mw): 8,000): the numerical valuedescribed for each repeating unit means mol %): 100 parts by mass

Photoacid generators shown below: 12 parts by mass (the mass ratio is0.5:0.5 from left to right)

Quenchers shown below: 5 parts by mass (mass ratio is 0.3:0.7 from leftto right.)

Hydrophobic resins shown below: 5 parts by mass (the mass ratio is0.8:0.2 from top to bottom).

Between the following hydrophobic resins, the upper hydrophobic resinhas a weight-average molecular weight (Mw) of 8,000, and the lowerhydrophobic resin has a weight-average molecular weight (Mw) of 6,000.In each of the hydrophobic resins, the numerical value described foreach repeating unit means molar ratio.

Solvent:

Propylene glycol monomethyl ether acetate (PGMEA): 3 parts by mass

Cyclohexanone: 600 parts by mass

γ-Butyrolactone (γ-BL): 100 parts by mass

<Resist Composition 3>

Acid-decomposable resin (resin represented by the following formula(weight-average molecular weight (Mw): 8,000): the numerical valuedescribed for each repeating unit means mol %): 100 parts by mass

Photoacid generator shown below: 15 parts by mass

Quenchers shown below: 7 parts by mass (the mass ratio is 1:1 from leftto right.)

Hydrophobic resins shown below: 20 parts by mass (the mass ratio is 3:7from top to bottom.)

Between the following hydrophobic resins, the upper hydrophobic resinhas a weight-average molecular weight (Mw) of 10,000, and the lowerhydrophobic resin has a weight-average molecular weight (Mw) of 7,000.In the lower hydrophobic resin, the molar ratio of each of the repeatingunits is 0.67:0.33 from left to right.

Solvent:

Propylene glycol monomethyl ether acetate (PGMEA): 50 parts by mass

Propylene glycol monomethyl ether (PGME): 100 parts by mass

2-Heptanone: 100 parts by mass

γ-Butyrolactone (γ-BL): 500 parts by mass

<Resist Composition 4>

Resin having repeating unit represented by the following formula: 2.9%by mass with respect to total mass of resist composition

Photoacid generator shown below: 0.2% by mass with respect to total massof resist

Composition

Photoacid generator shown below: 0.1% by mass with respect to total massof resist composition

Hydrophobic resin having repeating units shown below: 0.02% by mass withrespect to total mass of resist composition

Quencher shown below: 0.25% by mass with respect to total mass of resistcomposition

PGMEA: 67.7% by mass with respect to total mass of resist composition

CyHx: balance with respect to total mass of resist composition

<Resist Composition 5>

Resin having repeating units shown below (molar ratio of each of therepeating units is 10/30/10/35/15 from left): 2.8% by mass with respectto total mass of resist composition

Hydrophobic resin having repeating units represented by the followingformulae (molar ratio of each of the repeating units is 90/8/2 fromleft): 0.14% by mass with respect to total mass of resist composition

Photoacid generator shown below: 0.37% by mass with respect to totalmass of resist composition

Photoacid generator shown below: 0.21% by mass with respect to totalmass of resist composition

Quencher shown below: 0.026% by mass with respect to total mass ofresist composition

PGMEA: 93% by mass with respect to total mass of resist composition

GBL: balance with respect to total mass resist composition

<Resist Composition 6>

Resin having repeating units represented by the following formulae (amolar ratio of each of the repeating units is 63.33/25.25/11.49 fromleft, Mw is about 21,000): 13% by mass with respect to total mass ofresist composition

Photoacid generator shown below: 0.32% by mass with respect to totalmass of resist composition

Quencher shown below: 0.018% by mass with respect to total mass ofresist composition

Compound shown below: 0.005% by mass with respect to total mass ofresist composition

Compound shown below: 0.57% by mass with respect to total mass of resistcomposition

PGMEA: 68% by mass with respect to total mass of resist composition

3-Ethoxyethyl propionate: balance with respect to total mass of resistcomposition

Each of the above resist compositions was used after the abovecomponents were mixed together and then filtered through a filter madeof UPE (ultra-high-molecular-weight polyethylene) having a pore size of0.1 μm and a filter made of nylon having a pore size of 0.04

The weight-average molecular weight (Mw) of each of the resistcompositions is a value determined by a GPC method by usingtetrahydrofuran (THF) as a developing solvent and expressed in terms ofpolystyrene.

Specifically, the following device was used.

Device: HLC-8120 manufactured by Tosoh Corporation

Column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation

[Affinity Between Chemical Liquid and Acid-Decomposable Resin]

The affinity between each of the chemical liquids and the resin wasmeasured using a pulsed nuclear magnetic resonance-type particleinterface characteristic evaluator (trade name: include “Acorn Area”,manufactured by Xigo Nanotools).

As a first test solution, a solution was used which was obtained bydissolving the acid-decomposable resin contained in each of the actinicray-sensitive or radiation-sensitive resin compositions in each of thechemical liquids at 0.5%.

As a second test solution, a solution was used which was obtained bydissolving the acid-decomposable resin contained in each of the actinicray-sensitive or radiation-sensitive resin compositions in each of thechemical liquids at 3.0%.

For each of the solutions, τ0, τ1, and τ2 were determined under thecondition of 25° C., and Rsq1 and SRsq were calculated. The results wereclassified based on the following standards, and shown in Table 1.

Rsg1

A: Rsq1 was higher than 0.5.

B: Rsq1 was equal to or lower than 0.5.

SRsq

A: SRsq was higher than −1.

B: SRsq was equal to or lower than −1.

[Evaluation of Defect Inhibition Performance of Chemical Liquid]

The defect inhibition performance of the chemical liquid was evaluatedby the following method. For the following test, a coater/developer“RF^(3S)” manufactured by SOKUDO Co., Ltd was used.

First, a bare silicon substrate (silicon wafer) having a diameter ofabout 300 mm (12 inches) was prepared. Then, the silicon wafer wascoated with an antireflection film composition and baked for 60 secondsat 200° C., thereby forming an antireflection film (thickness: 89 nm).Thereafter, each of the chemical liquids was added dropwise to theantireflection film, and the antireflection film was continuously coatedwith an actinic ray-sensitive or radiation-sensitive resin compositionand baked for 60 seconds at 90° C., thereby forming a resist film havinga thickness of 85 nm. Subsequently, the resist film was exposed andbaked for 60 seconds at 100° C. Then, the resist film obtained afterexposure was developed using an organic solvent-based developer. Theresist film obtained after development was baked for 60 seconds at 100°C., thereby obtaining a pattern.

By using a wafer inspection device “UVision 5” manufactured by AppliedMaterials, Inc., the image of the pattern was captured, and the obtainedimage was analyzed using a full automatic defect review device“SEMVision G4” manufactured by Applied Materials, Inc., thereby countingthe number of pattern defects per unit area. In the presentspecification, the number of pattern defects means the number ofresidues in an unexposed portion (described as “Residue in unexposedportion” in Table 1), the number of defects in the form of bridgebetween patterns (number of BRIDGE defects, described as “BRIDGE” inTable 1), and the number of sites where pattern collapse occurs(described as “Pattern collapse” in Table 1). Table 1 shows the resultsevaluated based on the following standards.

-   -   AA: The number of pattern defects was less than 30.    -   A: The number of pattern defects was equal to or greater than 30        and less than 60.    -   B: The number of pattern defects was equal to or greater than 60        and less than 90.    -   C: The number of pattern defects was equal to or greater than 90        and less than 120.    -   D: The number of pattern defects was equal to or greater than        120.

[Resist Saving Properties of Resist Composition]

The resist saving properties of the resist composition after the coatingof the chemical liquid were evaluated by the following method. In thepresent specification, having excellent resist saving properties meansthat the uniformity and the film thickness controllability areexcellent.

<Uniformity>

First, as a control, a silicon wafer comprising an antireflection filmand having a diameter of about 30 cm (12 inches) was directly coatedwith the resist composition. The coating was performed using a spincoater (trade name: “LITHIUS”, manufactured by Tokyo Electron Limited).The obtained resist film was baked at 90° C. For the baked resist film,a 59-point map was measured using a film thickness measurement apparatusLambda Ace manufactured by SCREEN Holdings Co., Ltd. so as to confirmthat no coating mottle occurred. For checking the coating mottle, 59circular measurement spots were extracted from the resist film to bemeasured, the thickness of the resist film was measured at each of themeasurement spots, and the measured thicknesses were two-dimensionallyarranged for the respective measurement spots and observed. At thistime, in a case where no unevenness was found in the resist filmthickness, it was considered that there was no coating mottle.

Then, another silicon wafer comprising an antireflection film and havinga diameter of about 30 cm (12 inches) was prepared, and each of thechemical liquids was added dropwise thereto. Thereafter, the wafer wascoated with the same amount of the resist composition used for thecontrol, and baked at 90° C. The obtained resist film was observed bythe same method as described above so as to confirm that no coatingmottle occurred. Subsequently, the same test as above was performed byreducing the amount of the used resist composition such that the amountof the resist composition became 50% by mass and 30% by mass of theamount of the resist composition used for the control, and whether thecoating mottle occurred was investigated.

The results were evaluated based on the following standards, and shownin Table 2.

A: Even though the amount of the used resist composition was reduced andbecame 30% by mass and 50% by mass of the amount of the resistcomposition used for the control, no coating mottle occurred.

B: Even though the amount of the used resist composition was reduced andbecame 50% by mass of the amount of the resist composition used for thecontrol, no coating mottle occurred. However, in a case where the amountof the used resist composition was reduced and became 30% by mass of theamount of the resist composition used for the control, a coating mottleoccurred.

C: In a case where the amount of the used resist composition was reducedand became 30% by mass and 50% by mass of the amount of the resistcomposition used for the control, a coating mottle occurred.

<Film Thickness Controllability>

Each of the chemical liquids was added dropwise to a silicon wafercomprising an antireflection film and having a diameter of about 30 cm(12 inches). Then, the wafer was directly coated with the aforementionedresist composition such that the thickness of the obtained resist filmbecame 8.5 nm. The coating was performed using a spin coater (tradename: “LITHIUS”, manufactured by Tokyo Electron Limited). The obtainedresist film was baked at 90° C. For the baked resist film, a 59-pointmap was measured using a film thickness measurement apparatus Lambda Acemanufactured by SCREEN Holdings Co., Ltd., and a standard deviation(hereinafter, referred to as “σ” as well) of the thickness of the resistfilm was determined. Subsequently, from the standard deviation, 3σ wasdetermined. The results were evaluated based on the following standards,and shown in Table 1.

A: 3σ was less than 0.15 nm.

B: 3σ was equal to or greater than 0.15 nm and less than 0.2 nm.

C: 3σ was equal to or greater than 0.2 nm.

TABLE 1-1-1 Chemical liquid Composition of mixture First organic solventContent Molar mass Vapor pressure Surface tension δh δd Type (% by mass)(g/mol) (Pa) (mN/m) (MPa)^(0.5) (MPa)^(0.5) Example 1 DBCPN 95 130.2 40030.2 4.2 16.6 Example 2 HBM 95 118.1 360 29.1 12.2 16.5 Example 3 EL 95118.1 333 29.8 12.5 16.0 Example 4 Example 5 Example 6 Example 7 HBM 95118.1 360 29.1 12.2 16.5 Example 8 EL 95 118.1 333 29.8 12.5 16.0Example 9 CyHx 70 98.1 507 34.1 5.1 17.8 Example 10 PGMEA 90 132.2 49327.9 9.8 15.6 Example 11 PGMEA 95 132.2 493 27.9 9.8 15.6 Example 12 MMP95 98.1 320 30.2 8.1 15.9 Example 13 MMP 97 98.1 320 30.2 8.1 15.9Example 14 Example 15 Example 16 Example 17 Example 18 CyHx 95 98.1 50734.1 5.1 17.8 Example 19 HBM 95 118.1 360 29.1 12.2 16.5 Example 20 EL95 118.1 333 29.8 12.5 16.0 Example 21 PGMEA 80 132.2 493 27.9 9.8 15.6Example 22 PGMEA 85 132.2 493 27.9 9.8 15.6 Example 23 PGMEA 90 132.2493 27.9 9.8 15.6 Example 24 PGMEA 93 132.2 493 27.9 9.8 15.6 Example 25MMP 95 98.1 320 30.2 8.1 15.9 Example 26 MMP 97 98.1 320 30.2 8.1 15.9Example 27 DBCPN 80 130.2 400 30.2 4.2 16.6 Example 28 Example 29Example 30 HBM 95 118.1 360 29.1 12.2 16.5 Example 31 EL 95 118.1 33329.8 12.5 16.0 Example 32 CyHx 80 98.1 507 34.1 5.1 17.8 Example 33PGMEA 80 132.2 493 27.9 9.8 15.6 Example 34 Example 35 Example 36 HBM 95118.1 360 29.1 12.2 16.5 Example 37 EL 95 118.1 333 29.8 12.5 16.0Example 38 CyHx 80 98.1 507 34.1 5.1 17.8 Example 39 PGMEA 80 132.2 49327.9 9.8 15.6 Example 40 DBCPN 80 130.2 400 30.2 4.2 16.6

TABLE 1-1-2 Chemical liquid Composition of mixture First organic solventContent Molar mass Vapor pressure Surface tension δh δd Type (% by mass)(g/mol) (Pa) (mN/m) (MPa)^(0.5) (MPa)^(0.5) Example 1 Example 2 Example3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10Example 11 Example 12 Example 13 Example 14 Example 15 Example 16Example 17 Example 18 Example 19 Example 20 Example 21 Example 22Example 23 Example 24 Example 25 Example 26 Example 27 Example 28Example 29 Example 30 Example 31 Example 32 Example 33 Example 34Example 35 Example 36 Example 37 Example 38 Example 39 Example 40

TABLE 1-1-3 Chemical liquid Composition of mixture First organic solventContent Molar mass Vapor pressure Surface tension δh δd Type (% by mass)(g/mol) (Pa) (mN/m) (MPa)^(0.5) (MPa)^(0.5) Example 1 Example 2 Example3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10Example 11 Example 12 Example 13 Example 14 Example 15 Example 16Example 17 Example 18 Example 19 Example 20 Example 21 Example 22Example 23 Example 24 Example 25 Example 26 Example 27 Example 28Example 29 Example 30 Example 31 Example 32 Example 33 Example 34Example 35 Example 36 Example 37 Example 38 Example 39 Example 40

TABLE 1-1-4 Chemical liquid Composition of mixture Second organicsolvent Content Molar mass Vapor pressure Surface tension δh δd Type (%by mass) (g/mol) (Pa) (mN/m) (MPa)^(0.5) (MPa)^(0.5) Example 1 Example 2Example 3 Example 4 CyPn 30 84.1 1,520 33.8 4.8 17.8 Example 5 nBA 50116.2 1,200 24.8 6.3 15.8 Example 6 nBA 80 116.2 1,200 24.8 6.3 15.8Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example13 Example 14 nBA 60 116.2 1,200 24.8 6.3 15.8 Example 15 PGME 50 90.11,453 27.6 13.3 16.4 Example 16 CyPn 50 84.1 1,520 33.8 4.8 17.8 Example17 CyPn 10 84.1 1,520 33.8 4.8 17.8 Example 18 Example 19 Example 20Example 21 Example 22 Example 23 Example 24 Example 25 Example 26Example 27 Example 28 PGME 50 90.1 1,453 27.6 13.3 16.4 Example 29 CyPn50 84.1 1,520 33.8 4.8 17.8 Example 30 Example 31 Example 32 Example 33Example 34 PGME 50 90.1 1,453 27.6 13.3 16.4 Example 35 CyPn 50 84.11,520 33.8 4.8 17.8 Example 36 Example 37 Example 38 Example 39 Example40

TABLE 1-1-5 Chemical liquid Composition of mixture Ether-based Thirdorganic solvent compound Content Molar mass Vapor pressure Surfacetension δh δd Content Type (% by mass) (g/mol) (Pa) (mN/m) (Mpa)^(0.5)(Mpa)^(0.5) (mass ppm) Example 1 GBL 5 86.1 147 44.1 7.0 17.4 0 Example2 GBL 5 86.1 147 44.1 7.0 17.4 0 Example 3 GBL 5 86.1 147 44.1 7.0 17.40 Example 4 GBL 70 86.1 147 44.1 7.0 17.4 0 Example 5 GBL 50 86.1 14744.1 7.0 17.4 0 Example 6 GBL 20 86.1 147 44.1 7.0 17.4 0 Example 7 DMSO5 78.1 13 43.6 10.2 18.4 0 Example 8 DMSO 5 78.1 13 43.6 10.2 18.4 0Example 9 DMSO 30 78.1 13 43.6 10.2 18.4 0 Example 10 DMSO 10 78.1 1343.6 10.2 18.4 0 Example 11 DMSO 5 78.1 13 43.6 10.2 18.4 0 Example 12DMSO 5 78.1 13 43.6 10.2 18.4 0 Example 13 DMSO 3 78.1 13 43.6 10.2 18.40 Example 14 DMSO 40 78.1 13 43.6 10.2 18.4 0 Example 15 DMSO 50 78.1 1343.6 10.2 18.4 0 Example 16 DMSO 50 78.1 13 43.6 10.2 18.4 0 Example 17DMSO 90 78.1 13 43.6 10.2 18.4 0 Example 18 PC 5 102.1 53 40.9 6.5 17.30 Example 19 PC 5 102.1 53 40.9 6.5 17.3 0 Example 20 PC 5 102.1 53 40.96.5 17.3 0 Example 21 PC 20 102.1 53 40.9 6.5 17.3 0 Example 22 PC 15102.1 53 40.9 6.5 17.3 0 Example 23 PC 10 102.1 53 40.9 6.5 17.3 0Example 24 PC 7 102.1 53 40.9 6.5 17.3 0 Example 25 PC 5 102.1 53 40.96.5 17.3 0 Example 26 PC 3 102.1 53 40.9 6.5 17.3 0 Example 27 PC 20102.1 53 40.9 6.5 17.3 0 Example 28 PC 50 102.1 53 40.9 6.5 17.3 0Example 29 PC 50 102.1 53 40.9 6.5 17.3 0 Example 30 EC 5 88.1 67 41.58.0 18.1 0 Example 31 EC 5 88.1 67 41.5 8.0 18.1 0 Example 32 EC 20 88.167 41.5 8.0 18.1 0 Example 33 EC 20 88.1 67 41.5 8.0 18.1 0 Example 34EC 50 88.1 67 41.5 8.0 18.1 0 Example 35 EC 50 88.1 67 41.5 8.0 18.1 0Example 36 NMP 5 99.1 40 41.3 7.2 18.0 0 Example 37 NMP 5 99.1 40 41.37.2 18.0 0 Example 38 NMP 20 99.1 40 41.3 7.2 18.0 0 Example 39 NMP 2099.1 40 41.3 7.2 18.0 0 Example 40 NMP 20 99.1 40 41.3 7.2 18.0 0

TABLE 1-1-6 Chemical liquid Resist composition Physical Evaluationproperties of Resist saving Defect inhibition mixture propertiesperformance Vapor Surface Film Residue in pressure tension Affnitythickness Pattern unexposed (Pa) (mN/m) Type Rsq1 SRsq Uniformitycontrollability collapse portion BRIDGE Example 1 381 31.2 1 A A A A AAAA AA Example 2 346 30.1 1 A B A A AA A AA Example 3 321 30.8 1 A B A AAA A AA Example 4 565 41.0 1 A A A A AA AA B Example 5 595 35.9 1 A A AA AA AA B Example 6 934 29.7 1 A A A B AA AA B Example 7 334 30.2 1 A BA A AA A AA Example 8 310 30.8 1 A B A A AA A AA Example 9 334 37.4 1 AA A A AA AA A Example 10 417 30.4 1 A A A A AA AA A Example 11 454 29.21 A A A A AA AA AA Example 12 301 31.0 1 A A A A AA AA AA Example 13 30930.7 1 A A A A AA AA AA Example 14 609 34.2 1 A A A A AA AA B Example 15682 36.2 1 B B A A AA B B Example 16 739 38.9 1 A A A A AA AA B Example17 154 42.7 1 A A A A A A B Example 18 485 34.4 1 A A A A AA AA AAExample 19 342 29.8 1 A B A A AA A AA Example 20 317 30.4 1 A B A A AA AAA Example 21 386 31.1 1 A A A A AA AA A Example 22 411 30.3 1 A A A AAA AA AA Example 23 438 29.5 1 A A A A AA AA AA Example 24 454 29.1 1 AA A A AA AA AA Example 25 307 30.7 1 A A A A AA AA AA Example 26 31230.5 1 A A A A AA AA AA Example 27 316 32.8 1 A A A A AA AA A Example 28797 33.8 1 B B A A AA B B Example 29 857 37.0 1 A A A A AA AA B Example30 341 29.9 1 A B A A AA B AA Example 31 316 30.6 1 A B A B AA A AAExample 32 411 35.7 1 A A A A AA AA A Example 33 377 31.6 1 A A A A AAAA A Example 34 752 34.6 1 B B A A AA B B Example 35 810 37.6 1 A A A AAA AA B Example 36 341 29.8 1 A B A A AA A AA Example 37 316 30.5 1 A BA A AA A AA Example 38 414 35.5 1 A A A A AA AA A Example 39 380 31.2 1A A A A AA AA A Example 40 311 32.9 1 A A A A AA AA A

TABLE 1-1-7 Resist composition Evaluation Resist saving Defectinhibition properties performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 1 2 A A A A AA AA AA Example 2 2 A A A A AA AA AAExample 3 2 A A A A AA AA AA Example 4 2 A A A A AA AA B Example 5 2 A AA A AA AA B Example 6 2 A A B B AA AA B Example 7 2 A A A A AA AA AAExample 8 2 A A A A AA AA AA Example 9 2 A A A A AA AA A Example 10 2 AB A A AA A A Example 11 2 A A A A AA AA AA Example 12 2 A A A A AA AA AAExample 13 2 A A A A AA AA AA Example 14 2 A A A A AA AA B Example 15 2B B A A AA B B Example 16 2 A A A A AA AA B Example 17 2 A A A A A A BExample 18 2 A A A A AA AA AA Example 19 2 A A A A AA AA AA Example 20 2A A A A AA AA AA Example 21 2 A B A A AA A A Example 22 2 A A A A AA AAAA Example 23 2 A A A A AA AA AA Example 24 2 A A A A AA AA AA Example25 2 A A A A AA AA AA Example 26 2 A A A A AA AA AA Example 27 2 A A A AAA AA A Example 28 2 B B A A AA B B Example 29 2 A A A A AA AA B Example30 2 A A A A AA AA AA Example 31 2 A A A A AA AA AA Example 32 2 A A A AAA AA A Example 33 2 A B A A AA A A Example 34 2 B B A A AA B B Example35 2 A A A A AA AA B Example 36 2 A A A A AA AA AA Example 37 2 A A A AAA AA AA Example 38 2 A A A A AA AA A Example 39 2 A A A A AA A AExample 40 2 A A A A AA AA A

TABLE 1-1-8 Resist composition Evaluation Resist saving Defectinhibition properties performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 1 3 A A A A AA AA AA Example 2 3 A B A A AA A AAExample 3 3 A A A A AA AA AA Example 4 3 A A A A AA AA B Example 5 3 A AA A AA AA B Example 6 3 A A B B AA AA B Example 7 3 A B A A AA A AAExample 8 3 A A A A AA AA AA Example 9 3 A A A A AA AA A Example 10 3 AB A A AA AA A Example 11 3 A A A A AA AA AA Example 12 3 A A A A AA AAAA Example 13 3 A A A A AA AA AA Example 14 3 A A A A AA AA B Example 153 A A A A AA AA B Example 16 3 A A A A AA AA B Example 17 3 A A A A A AB Example 18 3 A A A A AA AA AA Example 19 3 A B A A AA A AA Example 203 A A A A AA AA AA Example 21 3 A B A A AA A A Example 22 3 A A A A AAAA AA Example 23 3 A A A A AA AA AA Example 24 3 A A A A AA AA AAExample 25 3 A A A A AA AA AA Example 26 3 A A A A AA AA AA Example 27 3A A A A AA AA A Example 28 3 A A A A AA AA B Example 29 3 A A A A AA AAB Example 30 3 A A A A AA AA AA Example 31 3 A A A A AA AA AA Example 323 A A A A AA AA A Example 33 3 A B A A AA A A Example 34 3 A A A A AA AAB Example 35 3 A A A A AA AA B Example 36 3 B B A A AA A AA Example 37 3A A A A AA AA AA Example 38 3 A A A A AA AA A Example 39 3 A B A A AA AA Example 40 3 A A A A AA AA A

TABLE 1-1-9 Resist composition Evaluation Resist saving propertiesDefect inhibition performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 1 4 B A A A AA A A Example 2 4 A A A A AA AA AAExample 3 4 A A A A AA AA AA Example 4 4 A A A A AA AA A Example 5 4 A AA A AA AA B Example 6 4 A A A B AA AA B Example 7 4 A A A A AA A AAExample 8 4 A A A A AA AA AA Example 9 4 A A A A AA AA A Example 10 4 AA A A AA AA AA Example 11 4 A A A A AA AA AA Example 12 4 A A A A AA AAAA Example 13 4 A A A A AA AA AA Example 14 4 A A A A AA AA B Example 154 A A A A AA AA B Example 16 4 A A A A AA AA B Example 17 4 A A A B A AB Example 18 4 A A A A AA AA AA Example 19 4 A B A A AA A AA Example 204 A A A A AA AA AA Example 21 4 A B A B AA A A Example 22 4 A A A A AAAA AA Example 23 4 A A A A AA AA AA Example 24 4 A A A A AA AA AAExample 25 4 A A A A AA AA AA Example 26 4 A A A A AA AA AA Example 27 4B A A A AA A A Example 28 4 A A A A AA AA B Example 29 4 A A A A AA AA BExample 30 4 A A A A AA AA AA Example 31 4 A A A A AA AA AA Example 32 4A A A A AA AA A Example 33 4 A A A A AA A A Example 34 4 A A A A AA AA BExample 35 4 A A A A AA AA B Example 36 4 B B A A AA A AA Example 37 4 AA A A AA AA AA Example 38 4 A A A A AA AA A Example 39 4 B A A A AA A AExample 40 4 B A A A AA AA A

TABLE 1-1-10 Resist composition Evaluation Resist saving propertiesDefect inhibition performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 1 5 B A A A AA A A Example 2 5 B A A A A A AExample 3 5 B A A A A A A Example 4 5 A A A A AA AA A Example 5 5 A A AA AA AA B Example 6 5 A A A B AA AA B Example 7 5 B A A A A A A Example8 5 B A A A A A A Example 9 5 A A A A AA AA A Example 10 5 A A A A AA AAAA Example 11 5 A A A A AA AA AA Example 12 5 A A A A AA AA AA Example13 5 A A A A AA AA AA Example 14 5 A A A A AA AA B Example 15 5 A A A AAA AA B Example 16 5 A A A A AA AA B Example 17 5 A A A B A A B Example18 5 A A A A AA AA AA Example 19 5 B A A A A A A Example 20 5 B A A A AA A Example 21 5 A B A B AA A A Example 22 5 A A A A AA AA AA Example 235 A A A A AA AA AA Example 24 5 A A A A AA AA AA Example 25 5 A A A A AAAA AA Example 26 5 A A A A AA AA AA Example 27 5 B A A A AA A A Example28 5 A A A A AA AA B Example 29 5 A A A A AA AA B Example 30 5 B A A A AA A Example 31 5 B A A A A A A Example 32 5 A A A A AA AA A Example 33 5A A A A AA A A Example 34 5 A A A A AA AA B Example 35 5 A A A A AA AA BExample 36 5 B B A A AA A AA Example 37 5 A A A A AA AA AA Example 38 5A A A A AA AA A Example 39 5 B A A A AA A A Example 40 5 B A A A AA AA A

TABLE 1-1-11 Resist composition Evaluation Resist saving propertiesDefect inhibition performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 1 6 B A A A AA AA A Example 2 6 A A A A AA AA AAExample 3 6 A A A A AA AA AA Example 4 6 A A A A AA AA A Example 5 6 A AA A AA AA B Example 6 6 A A A B AA AA B Example 7 6 A A A A AA A AAExample 8 6 A A A A AA AA AA Example 9 6 A A A A AA AA A Example 10 6 AA A A AA AA AA Example 11 6 A A A A AA AA AA Example 12 6 A A A A AA AAAA Example 13 6 A A A A AA AA AA Example 14 6 A A A A AA AA B Example 156 A A A A AA AA B Example 16 6 A A A A AA AA B Example 17 6 A A A B A AB Example 18 6 A A A A AA AA AA Example 19 6 A B A A AA A AA Example 206 A A A A AA AA AA Example 21 6 A B A B AA A A Example 22 6 A A A A AAAA AA Example 23 6 A A A A AA AA AA Example 24 6 A A A A AA AA AAExample 25 6 A A A A AA AA AA Example 26 6 A A A A AA AA AA Example 27 6B A A A AA A A Example 28 6 A A A A AA AA B Example 29 6 A A A A AA AA BExample 30 6 A A A A AA AA AA Example 31 6 A A A A AA AA AA Example 32 6A A A A AA AA A Example 33 6 A A A A AA A A Example 34 6 A A A A AA AA BExample 35 6 A A A A AA AA B Example 36 6 B B A A AA A AA Example 37 6 AA A A AA AA AA Example 38 6 A A A A AA AA A Example 39 6 B A A A AA A AExample 40 6 B A A A AA AA A

TABLE 1-2-1 Chemical liquid Composition of mixture First organic solventContent Molar mass Vapor pressure Surface tension δh δd Type (% by mass)(g/mol) (Pa) (mN/m) (Mpa)^(0.5) (Mpa)^(0.5) Example 41 Example 42Example 43 PGMEA 80 132.2 493 27.9 9.8 15.6 Example 44 PGMEA 80 132.2493 27.9 9.8 15.6 Example 45 CyHx 80 98.1 507 34.1 5.1 17.8 Example 46CyHx 40 98.1 507 34.1 5.1 17.8 Example 47 CyHx 80 98.1 507 34.1 5.1 17.8Example 48 CyHx 80 98.1 507 34.1 5.1 17.8 Example 49 CyHx 80 98.1 50734.1 5.1 17.8 Example 50 EL 70 118.1 333 29.8 12.5 16.0 Example 51 EL 90118.1 333 29.8 12.5 16.0 Example 52 EL 20 118.1 333 29.8 12.5 16.0Example 53 EL 40 118.1 333 29.8 12.5 16.0 Example 54 HBM 80 118.1 36029.1 12.2 16.5 Example 55 HBM 80 118.1 360 29.1 12.2 16.5 Example 56 HBM80 118.1 360 29.1 12.2 16.5 Example 57 DBCPN 80 130.2 400 30.2 4.2 16.6Example 58 DBCPN 80 130.2 400 30.2 4.2 16.6 Example 59 PGMEA 70 132.2493 27.9 9.8 15.6 Example 60 CyHx 30 98.1 507 34.1 5.1 17.8 Example 61DBCPN 60 130.2 400 30.2 4.2 16.6 Example 62 HBM 35 118.1 360 29.1 12.216.5 Example 63 EL 70 118.1 333 29.8 12.5 16.0 Example 64 HBM 25 118.1360 29.1 12.2 16.5 Example 65 HBM 25 118.1 360 29.1 12.2 16.5 Example 66HBM 35 118.1 360 29.1 12.2 16.5 Example 67 HBM 35 118.1 360 29.1 12.216.5 Example 68 HBM 35 118.1 360 29.1 12.2 16.5 Example 69 HBM 35 118.1360 29.1 12.2 16.5 Example 70 HBM 35 118.1 360 29.1 12.2 16.5 Example 71EL 30 118.1 333 29.8 12.5 16.0 Example 72 HBM 25 118.1 360 29.1 12.216.5 Example 73 HBM 25 118.1 360 29.1 12.2 16.5 Example 74 HBM 45 118.1360 29.1 12.2 16.5 Example 75 EL 30 118.1 333 29.8 12.5 16.0 Example 76HBM 25 118.1 360 29.1 12.2 16.5 Example 77 HBM 25 118.1 360 29.1 12.216.5 Example 78 PGMEA 50 132.2 493 27.9 9.8 15.6 Example 79 EGMEA 5098.1 380 30.7 8.1 15.9 Example 80 EGMEA 50 98.1 380 30.7 8.1 15.9

TABLE 1-2-2 Chemical liquid Composition of mixture First organic solventContent Molar mass Vapor pressure Surface tension δh δd Type (% by mass)(g/mol) (Pa) (mN/m) (Mpa)^(0.5) (Mpa)^(0.5) Example 41 Example 42Example 43 Example 44 Example 45 Example 46 Example 47 EL 20 118.1 33329.8 12.5 16.0 Example 48 HBM 20 118.1 360 29.1 12.2 16.5 Example 49DBCPN 20 130.2 400 30.2 4.2 16.6 Example 50 Example 51 Example 52 DBCPN80 130.2 400 30.2 4.2 16.6 Example 53 HBM 60 118.1 360 29.1 12.2 16.5Example 54 Example 55 Example 56 DBCPN 20 130.2 400 30.2 4.2 16.6Example 57 Example 58 Example 59 EL 10 118.1 333 29.8 12.5 16.0 Example60 PGMEA 60 132.2 493 27.9 9.8 15.6 Example 61 EL 30 118.1 333 29.8 12.516.0 Example 62 PGMEA 55 132.2 493 27.9 9.8 15.6 Example 63 Example 64CyHx 70 98.1 507 34.1 5.1 17.8 Example 65 DBCPN 70 130.2 400 30.2 4.216.6 Example 66 PGMEA 60 132.2 493 27.9 9.8 15.6 Example 67 PGMEA 55132.2 493 27.9 9.8 15.6 Example 68 PGMEA 45 132.2 493 27.9 9.8 15.6Example 69 PGMEA 40 132.2 493 27.9 9.8 15.6 Example 70 PGMEA 35 132.2493 27.9 9.8 15.6 Example 71 Example 72 CyHx 65 98.1 507 34.1 5.1 17.8Example 73 DBCPN 65 130.2 400 30.2 4.2 16.6 Example 74 PGMEA 45 132.2493 27.9 9.8 15.6 Example 75 Example 76 CyHx 65 98.1 507 34.1 5.1 17.8Example 77 DBCPN 65 130.2 400 30.2 4.2 16.6 Example 78 EL 10 118.1 33329.8 12.5 16.0 Example 79 PGMEA 50 132.2 493 27.9 9.8 15.6 Example 80 EL50 118.1 333 29.8 12.5 16.0

TABLE 1-2-3 Chemical liquid Composition of mixture First organic solventContent Molar mass Vapor pressure Surface tension δh δd Type (% by mass)(g/mol) (Pa) (mN/m) (Mpa)^(0.5) (Mpa)^(0.5) Example 41 Example 42Example 43 Example 44 Example 45 Example 46 Example 47 Example 48Example 49 Example 50 Example 51 Example 52 Example 53 Example 54Example 55 Example 56 Example 57 Example 58 Example 59 Example 60Example 61 Example 62 Example 63 Example 64 Example 65 Example 66Example 67 Example 68 Example 69 Example 70 Example 71 Example 72Example 73 Example 74 Example 75 Example 76 Example 77 Example 78 HBM 40118.1 360 29.1 12.2 16.5 Example 79 Example 80

TABLE 1-2-4 Chemical liquid Composition of mixture Second organicsolvent Content Molar mass Vapor pressure Surface tension δh δd Type (%by mass) (g/mol) (Pa) (mN/m) (Mpa)^(0.5) (Mpa)^(0.5) Example 41 PGME 5090.1 1,453 27.6 13.3 16.4 Example 42 CyPn 50 84.1 1,520 33.8 4.8 17.8Example 43 CyPn 20 84.1 1,520 33.8 4.8 17.8 Example 44 CyPn 20 84.11,520 33.8 4.8 17.8 Example 45 CyPn 20 84.1 1,520 33.8 4.8 17.8 Example46 CyPn 60 84.1 1,520 33.8 4.8 17.8 Example 47 Example 48 Example 49Example 50 PGME 30 90.1 1,453 27.6 13.3 16.4 Example 51 CyPn 10 84.11,520 33.8 4.8 17.8 Example 52 Example 53 Example 54 PGME 20 90.1 1,45327.6 13.3 16.4 Example 55 CyPn 20 84.1 1,520 33.8 4.8 17.8 Example 56Example 57 PGME 20 90.1 1,453 27.6 13.3 16.4 Example 58 CyPn 20 84.11,520 33.8 4.8 17.8 Example 59 CyPn 20 84.1 1,520 33.8 4.8 17.8 Example60 CyPn 10 84.1 1,520 33.8 4.8 17.8 Example 61 CyPn 10 84.1 1,520 33.84.8 17.8 Example 62 Example 63 CyPn 25 84.1 1,520 33.8 4.8 17.8 Example64 Example 65 Example 66 Example 67 Example 68 Example 69 Example 70Example 71 CyPn 60 84.1 1,520 33.8 4.8 17.8 Example 72 Example 73Example 74 Example 75 CyPn 60 84.1 1,520 33.8 4.8 17.8 Example 76Example 77 Example 78 Example 79 Example 80

TABLE 1-2-5 Chemical liquid Composition of mixture Third organic solventEther-based compound Content Molar mass Vapor pressure Surface tensionδh δd Content Type (% by mass) (g/mol) (Pa) (mN/m) (Mpa)^(0.5)(Mpa)^(0.5) (mass ppm) Example 41 NMP 50 99.1 40 41.3 7.2 18.0 0 Example42 NMP 50 99.1 40 41.3 7.2 18.0 0 Example 43 0 Example 44 5 Example 45 0Example 46 0 Example 47 0 Example 48 0 Example 49 0 Example 50 0 Example51 0 Example 52 0 Example 53 0 Example 54 0 Example 55 0 Example 56 0Example 57 0 Example 58 0 Example 59 0 Example 60 0 Example 61 0 Example62 DMSO 10 78.1 13 43.6 10.2 18.4 0 Example 63 DMSO 5 78.1 13 43.6 10.218.4 0 Example 64 DMSO 5 78.1 13 43.6 10.2 18.4 0 Example 65 DMSO 5 78.113 43.6 10.2 18.4 0 Example 66 GBL 5 86.1 147 44.1 7.0 17.4 0 Example 67GBL 10 86.1 147 44.1 7.0 17.4 0 Example 68 GBL 20 86.1 147 44.1 7.0 17.40 Example 69 GBL 25 86.1 147 44.1 7.0 17.4 0 Example 70 GBL 30 86.1 14744.1 7.0 17.4 0 Example 71 GBL 10 86.1 147 44.1 7.0 17.4 0 Example 72GBL 10 86.1 147 44.1 7.0 17.4 0 Example 73 GBL 10 86.1 147 44.1 7.0 17.40 Example 74 EC 10 88.1 67 41.5 8.0 18.1 0 Example 75 EC 10 88.1 67 41.58.0 18.1 0 Example 76 EC 10 88.1 67 41.5 8.0 18.1 0 Example 77 EC 1088.1 67 41.5 8.0 18.1 0 Example 78 5 Example 79 0 Example 80 0

TABLE 1-2-6 Chemical liquid Physical Resist composition properties ofEvaluation mixture Resist saving properties Defect inhibitionperformance Vapor Surface Film Residue in pressure tension Affinitythickness Pattern unexposed (Pa) (mN/m) Type Rsq1 SRsq Uniformitycontrollability collapse portion BRIDGE Example 41 780 34.1 1 B B A A AAB B Example 42 841 37.2 1 A A A A AA AA B Example 43 783 29.6 1 A A A AAA AA AA Example 44 783 29.6 1 A A A A A A A Example 45 735 34.0 1 A A AA AA AA AA Example 46 1,151 33.9 1 A A A B A AA A Example 47 477 33.4 1A A A A AA AA AA Example 48 481 33.2 1 A A A A AA AA AA Example 49 49033.5 1 A A A A AA AA AA Example 50 736 29.0 1 A B A A AA B AA Example 51493 30.3 1 A B A A AA A AA Example 52 386 30.1 1 A A A A AA AA A Example53 349 29.4 1 A B A A AA A B Example 54 630 28.7 1 A B B A AA A AAExample 55 661 30.3 1 A B A A AA A AA Example 56 367 29.3 1 A B A A AA AAA Example 57 679 29.5 1 A A A A AA AA AA Example 58 712 31.2 1 A A A AAA AA AA Example 59 764 29.7 1 A A A A AA AA AA Example 60 637 30.9 1 AA A A AA AA AA Example 61 539 30.6 1 A A A A AA AA AA Example 62 37330.7 1 A A A A AA AA AA Example 63 682 32.0 1 A B A A AA A AA Example 64443 33.6 1 A A A A AA AA AA Example 65 359 31.0 1 A A A A AA AA AAExample 66 420 29.5 1 A A A A AA AA AA Example 67 397 30.6 1 A A A A AAAA A Example 68 355 32.6 1 A A A A AA AA A Example 69 336 33.6 1 A A A AAA AA A Example 70 317 34.5 1 A A A A AA AA A Example 71 1,094 34.0 1 AA A B A AA A Example 72 433 34.2 1 A A A A AA AA AA Example 73 354 31.91 A A A A AA AA AA Example 74 374 30.3 1 A B A A AA A AA Example 751,088 33.7 1 A A A B A AA A Example 76 425 33.9 1 A A A A AA AA AAExample 77 344 31.5 1 A A A A AA AA AA Example 78 420 28.6 1 A B B A AAB A Example 79 417 29.5 1 A A A A AA AA AA Example 80 348 30.3 1 A B A AAA A AA

TABLE 1-2-7 Resist composition Evaluation Resist saving propertiesDefect inhibition performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 41 2 B B A A AA B B Example 42 2 A A A A AA AA BExample 43 2 A B A A AA A AA Example 44 2 A B A A A A B Example 45 2 A AA A AA AA AA Example 46 2 A A A B A AA A Example 47 2 A A A A AA AA AAExample 48 2 A A A A AA AA AA Example 49 2 A A A A AA AA AA Example 50 2B B A A AA B AA Example 51 2 A A A A AA AA AA Example 52 2 A A A A AA AAAA Example 53 2 A A A A AA AA B Example 54 2 B B B A AA A AA Example 552 A A A A AA AA AA Example 56 2 A A A A AA AA AA Example 57 2 B B A A AAB A Example 58 2 A A A A AA AA AA Example 59 2 A B A A AA A B Example 602 A B A A AA A AA Example 61 2 A A A A AA AA AA Example 62 2 A A A A AAAA AA Example 63 2 A A A A AA AA AA Example 64 2 A A A A AA AA AAExample 65 2 A A A A AA AA AA Example 66 2 A A A A AA AA AA Example 67 2A A A A AA AA A Example 68 2 A A A A AA AA A Example 69 2 A A A A AA AAA Example 70 2 A A A A AA AA A Example 71 2 A A A B A AA A Example 72 2A A A A AA AA A Example 73 2 A A A A AA AA AA Example 74 2 A A A A AA AAAA Example 75 2 A A A B A AA A Example 76 2 A A A A AA AA A Example 77 2A A A A AA AA AA Example 78 2 A B B A AA B AA Example 79 2 A A A A AA AAAA Example 80 2 A A A A AA AA AA

TABLE 1-2-8 Resist composition Evaluation Resist saving propertiesDefect inhibition performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 41 3 A A A A AA AA B Example 42 3 A A A A AA AA BExample 43 3 A B A A AA A AA Example 44 3 A B A A A A B Example 45 3 A AA A AA AA AA Example 46 3 A A A B A AA A Example 47 3 A A A A AA AA AAExample 48 3 A A A A AA AA AA Example 49 3 A A A A AA AA AA Example 50 3A A A A AA AA AA Example 51 3 A A A A AA AA AA Example 52 3 A A A A AAAA AA Example 53 3 A A A A AA AA B Example 54 3 A B B A AA A AA Example55 3 A B A B AA A AA Example 56 3 A B A A AA A AA Example 57 3 A A A AAA AA AA Example 58 3 A A A A AA AA AA Example 59 3 A A A A AA AA AAExample 60 3 A A A A AA AA AA Example 61 3 A A A A AA AA AA Example 62 3A A A A AA AA AA Example 63 3 A A A A AA AA AA Example 64 3 A A A A AAAA AA Example 65 3 A A A A AA AA AA Example 66 3 A A A A AA AA AAExample 67 3 A A A A AA AA A Example 68 3 A A A A AA AA A Example 69 3 AA A A AA AA A Example 70 3 A A A A AA AA A Example 71 3 A A A B A AA AExample 72 3 A A A A AA AA AA Example 73 3 A A A A AA AA AA Example 74 3A A A A AA AA AA Example 75 3 A A A B A AA A Example 76 3 A A A A AA AAAA Example 77 3 A A A A AA AA AA Example 78 3 A B B A AA B A Example 793 A A A A AA AA AA Example 80 3 A A A A AA AA AA

TABLE 1-2-9 Resist composition Evaluation Resist saving propertiesDefect inhibition performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 41 4 A A A A AA AA B Example 42 4 A A A A AA AA BExample 43 4 A B A A AA A AA Example 44 4 A B A A A A B Example 45 4 A AA A AA AA AA Example 46 4 A A A B A AA A Example 47 4 A A A A AA AA AAExample 48 4 A A A A AA AA AA Example 49 4 A A A A AA AA AA Example 50 4A A A A AA AA AA Example 51 4 A A A A AA AA AA Example 52 4 A A A A AAAA AA Example 53 4 A A A A AA AA B Example 54 4 A A A A AA A AA Example55 4 A A A B AA A AA Example 56 4 A A A A AA A AA Example 57 4 B A A AAA A A Example 58 4 B A A A AA AA A Example 59 4 A A A A AA AA AAExample 60 4 A A A A AA AA AA Example 61 4 A A A A AA AA AA Example 62 4A A A A AA AA AA Example 63 4 A A A A AA AA AA Example 64 4 A A A A AAAA AA Example 65 4 A A A A AA AA AA Example 66 4 A A A A AA AA AAExample 67 4 A A A A AA AA A Example 68 4 A A A A AA AA A Example 69 4 AA A A AA AA A Example 70 4 A A A A AA AA A Example 71 4 A A A B A AA AExample 72 4 A A A A AA AA AA Example 73 4 A A A A AA AA AA Example 74 4A A A A AA AA AA Example 75 4 A A A B A AA A Example 76 4 A A A A AA AAAA Example 77 4 A A A A AA AA AA Example 78 4 A B A A AA B A Example 794 A A A A AA AA AA Example 80 4 A A A A AA AA AA

TABLE 1-2-10 Resist composition Evaluation Resist saving propertiesDefect inhibition performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 41 5 A A A A AA AA B Example 42 5 A A A A AA AA BExample 43 5 A B A A AA A AA Example 44 5 A B A A A A B Example 45 5 A AA A AA AA AA Example 46 5 A A A B A AA A Example 47 5 A A A A AA AA AAExample 48 5 A A A A AA AA AA Example 49 5 A A A A AA AA AA Example 50 5A A A A AA AA AA Example 51 5 B A A A A A A Example 52 5 A A A A AA AAAA Example 53 5 A A A A AA AA B Example 54 5 A A A A AA A AA Example 555 A A A B AA A AA Example 56 5 B A A A A B A Example 57 5 B A A A AA B AExample 58 5 B A A A AA A A Example 59 5 A A A A AA AA AA Example 60 5 AA A A AA AA AA Example 61 5 B A A A AA B A Example 62 5 A A A A AA AA AAExample 63 5 A A A A AA AA AA Example 64 5 A A A A AA AA AA Example 65 5A A A A AA AA AA Example 66 5 B A A A AA B A Example 67 5 A A A A AA AAA Example 68 5 B A A A AA AA A Example 69 5 A A A A AA AA A Example 70 5A A A A AA AA A Example 71 5 A A A B A AA A Example 72 5 A A A A AA AAAA Example 73 5 A A A A AA AA AA Example 74 5 A A A A AA AA AA Example75 5 A A A B A AA A Example 76 5 A A A A AA AA AA Example 77 5 A A A AAA AA AA Example 78 5 A B A A AA B A Example 79 5 A A A A AA AA AAExample 80 5 A A A A AA AA AA

TABLE 1-2-11 Resist composition Evaluation Resist saving propertiesDefect inhibition performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 41 6 A A A A AA AA B Example 42 6 A A A A AA AA BExample 43 6 A B A A AA A AA Example 44 6 A B A A A A B Example 45 6 A AA A AA AA AA Example 46 6 A A A B A AA A Example 47 6 A A A A AA AA AAExample 48 6 A A A A AA AA AA Example 49 6 A A A A AA AA AA Example 50 6A A A A AA AA AA Example 51 6 A A A A AA AA AA Example 52 6 A A A A AAAA AA Example 53 6 A A A A AA AA B Example 54 6 A A A A AA A AA Example55 6 A A A B AA A AA Example 56 6 A A A A AA A AA Example 57 6 B A A AAA A A Example 58 6 B A A A AA AA A Example 59 6 A A A A AA AA AAExample 60 6 A A A A AA AA AA Example 61 6 A A A A AA AA AA Example 62 6A A A A AA AA AA Example 63 6 A A A A AA AA AA Example 64 6 A A A A AAAA AA Example 65 6 A A A A AA AA AA Example 66 6 A A A A AA AA AAExample 67 6 A A A A AA AA A Example 68 6 A A A A AA AA A Example 69 6 AA A A AA AA A Example 70 6 A A A A AA AA A Example 71 6 A A A B A AA AExample 72 6 A A A A AA AA AA Example 73 6 A A A A AA AA AA Example 74 6A A A A AA AA AA Example 75 6 A A A B A AA A Example 76 6 A A A A AA AAAA Example 77 6 A A A A AA AA AA Example 78 6 A B A A AA B A Example 796 A A A A AA AA AA Example 80 6 A A A A AA AA AA

TABLE 1-3-1 Chemical liquid Composition of mixture First organic solventContent Molar mass Vapor pressure Surface tension δh δd Type (% by mass)(g/mol) (Pa) (mN/m) (Mpa)^(0.5) (Mpa)^(0.5) Example 81 EGMEA 80 98.1 38030.7 8.1 15.9 Example 82 EGMEA 80 98.1 380 30.7 8.1 15.9 Example 83EGMEA 90 98.1 380 30.7 8.1 15.9 Example 84 EGMEA 90 98.1 380 30.7 8.115.9 Example 85 EGMEA 90 98.1 380 30.7 8.1 15.9 Example 86 MMP 50 98.1320 30.2 8.1 15.9 Example 87 MMP 80 98.1 320 30.2 8.1 15.9 Example 88MMP 80 98.1 320 30.2 8.1 15.9 Example 89 MMP 90 98.1 320 30.2 8.1 15.9Example 90 MMP 90 98.1 320 30.2 8.1 15.9 Example 91 MMP 90 98.1 320 30.28.1 15.9 Example 92 EEP 30 160 27.2 6.9 16.0 Comparative Example 1Comparative PGMEA 18 132.2 493 27.9 9.8 15.6 Example 2 Comparative CyHx20 98.1 507 34.1 5.1 17.8 Example 3 Comparative PGMEA 50 132.2 493 27.99.8 15.6 Example 4 Comparative PGMEA 50 132.2 493 27.9 9.8 15.6 Example5 Example 93 MMP 5 98.1 320 30.2 8.1 15.9 Example 94 MMP 30 98.1 32030.2 8.1 15.9

TABLE 1-3-2 Chemical liquid Composition of mixture First organic solventContent Molar mass Vapor pressure Surface tension δh δd Type (% by mass)(g/mol) (Pa) (mN/m) (Mpa)^(0.5) (Mpa)^(0.5) Example 81 DBCPN 20 130.2400 30.2 4.2 16.6 Example 82 Example 83 Example 84 Example 85 Example 86PGMEA 50 132.2 493 27.9 9.8 15.6 Example 87 Example 88 DBCPN 20 130.2400 30.2 4.2 16.6 Example 89 Example 90 Example 91 Example 92 EL 70118.1 333 29.8 12.5 16.0 Comparative Example 1 Comparative Example 2Comparative PGMEA 80 132.2 493 27.9 9.8 15.6 Example 3 Comparative EL 10118.1 333 29.8 12.5 16.0 Example 4 Comparative EL 50 118.1 333 29.8 12.516.0 Example 5 Example 93 PGMEA 95 132.2 493 27.9 9.8 15.6 Example 94

TABLE 1-3-3 Chemical liquid Composition of mixture First organic solventContent Molar mass Vapor pressure Surface tension δh δd Type (% by mass)(g/mol) (Pa) (mN/m) (Mpa)^(0.5) (Mpa)^(0.5) Example 81 Example 82Example 83 Example 84 Example 85 Example 86 Example 87 Example 88Example 89 Example 90 Example 91 Example 92 Comparative Example 1Comparative Example 2 Comparative Example 3 Comparative HBM 40 118.1 36029.1 12.2 16.5 Example 4 Comparative Example 5 Example 93 Example 94

TABLE 1-3-4 Chemical liquid Composition of mixture Second organicsolvent Content Molar mass Vapor pressure Surface tension δh δd Type (%by mass) (g/mol) (Pa) (mN/m) (Mpa)^(0.5) (Mpa)^(0.5) Example 81 Example82 PGME 20 90.1 1,453 27.6 13.3 16.4 Example 83 Example 84 Example 85Example 86 Example 87 PGME 20 90.1 1,453 27.6 13.3 16.4 Example 88Example 89 Example 90 Example 91 Example 92 Comparative PGME 60 90.11,453 27.6 13.3 16.4 Example 1 Comparative PGME 42 90.1 1,453 27.6 13.316.4 Example 2 Comparative Example 3 Comparative Example 4 ComparativeExample 5 Example 93 Example 94 PGME 70 90.1 1453 27.6 13.3 16.4

TABLE 1-3-5 Chemical liquid Composition of mixture Third organic solventEther-based compound Content Molar mass Vapor pressure Surface tensionδh δd Content Type (% by mass) (g/mol) (Pa) (mN/m) (Mpa)^(0.5)(Mpa)^(0.5) (mass ppm) Example 81 0 Example 82 0 Example 83 GBL 10 86.1147 44.1 7.0 17.4 0 Example 84 DMSO 10 78.1 13 43.6 10.2 18.4 0 Example85 PC 10 102.1 53 40.9 6.5 17.3 0 Example 86 0 Example 87 0 Example 88 0Example 89 GBL 10 86.1 147 44.1 7.0 17.4 0 Example 90 DMSO 10 78.1 1343.6 10.2 18.4 0 Example 91 PC 10 102.1 53 40.9 6.5 17.3 0 Example 92 0Comparative GBL 40 86.1 147 44.1 7.0 17.4 0 Example 1 Comparative GBL 4086.1 147 44.1 7.0 17.4 0 Example 2 Comparative 0 Example 3 Comparative10 Example 4 Comparative 0 Example 5 Example 93 0 Example 94 0

TABLE 1-3-6 Chemical liquid Resist composition Physical properties ofEvaluation mixture Defect inhibition performance Vapor Resist savingproperties Residue in pressure Surface tension Affinity Film thicknessPattern unexposed (Pa) (mN/m) Type Rsq1 SRsq Uniformity controllabilitycollapse portion BRIDGE Example 81 366 30.6 1 A A A A AA AA AA Example82 594 30.0 1 A B A A AA A AA Example 83 336 32.2 1 A A A A AA AA AAExample 84 318 32.3 1 A A A A AA AA AA Example 85 330 31.7 1 A A A A AAAA AA Example 86 394 29.2 1 A A A A AA AA AA Example 87 562 29.6 1 A B AA AA A AA Example 88 333 30.2 1 A A A A AA AA AA Example 89 300 31.8 1 AA A A AA AA AA Example 90 282 31.8 1 A A A A AA AA AA Example 91 29431.2 1 A A A A AA AA AA Example 92 333 29.8 1 A B A A AA A AAComparative 916 34.4 1 B B A C AA D B Example 1 Comparative 762 34.8 1 BB A A AA D B Example 2 Comparative 497 29.5 1 A A C A AA AA AA Example 3Comparative 420 28.6 1 A B B C A D A Example 4 Comparative 409 28.9 1 AB B C AA B A Example 5 Example 93 482 28.1 1 A B B B AA B A Example 941,133 28.3 1 B B B B AA B B

TABLE 1-3-7 Resist composition Evaluation Resist saving propertiesDefect inhibition performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 81 2 A A A A AA AA AA Example 82 2 A A A A AA AAAA Example 83 2 A A A A AA AA AA Example 84 2 A A A A AA AA AA Example85 2 A A A A AA AA AA Example 86 2 A A A A AA AA AA Example 87 2 A A A AAA AA AA Example 88 2 A A A A AA AA AA Example 89 2 A A A A AA AA AAExample 90 2 A A A A AA AA AA Example 91 2 A A A A AA AA AA Example 92 2A A A A AA AA AA Comparative 2 B B A C AA D B Example 1 Comparative 2 BB A A AA D B Example 2 Comparative 2 A A C A AA AA AA Example 3Comparative 2 A B B A A C A Example 4 Comparative 2 A B B C AA B AExample 5 Example 93 2 A B B B AA B A Example 94 2 B B B B AA B B

TABLE 1-3-8 Resist composition Evaluation Resist saving propertiesDefect inhibition performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 81 3 A A A A AA AA AA Example 82 3 A A A A AA AAAA Example 83 3 A A A A AA AA AA Example 84 3 A A A A AA AA AA Example85 3 A A A A AA AA AA Example 86 3 A A A A AA AA AA Example 87 3 A A A AAA AA AA Example 88 3 A A A A AA AA AA Example 89 3 A A A A AA AA AAExample 90 3 A A A A AA AA AA Example 91 3 A A A A AA AA AA Example 92 3A A A A AA AA AA Comparative 3 A A A C AA AA B Example 1 Comparative 3 AB A A AA C B Example 2 Comparative 3 A B A A AA C AA Example 3Comparative 3 A B B A A C A Example 4 Comparative 3 A B B C AA B AExample 5 Example 93 3 A A B B AA B A Example 94 3 A B B B AA B B

TABLE 1-3-9 Resist composition Evaluation Resist saving propertiesDefect inhibition performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 81 4 A A A A AA AA AA Example 82 4 A A A A AA AAAA Example 83 4 A A A A AA AA AA Example 84 4 A A A A AA AA AA Example85 4 A A A A AA AA AA Example 86 4 A A A A AA AA AA Example 87 4 A A A AAA AA AA Example 88 4 A A A A AA AA AA Example 89 4 A A A A AA AA AAExample 90 4 A A A A AA AA AA Example 91 4 A A A A AA AA AA Example 92 4A A A A AA AA AA Comparative 4 A A A C AA AA B Example 1 Comparative 4 AA A B AA AA B Example 2 Comparative 4 B A A A AA A AA Example 3Comparative 4 A A A B A AA A Example 4 Comparative 4 A A A C A AA AExample 5 Example 93 4 A A A B AA AA A Example 94 4 A A A B AA AA B

TABLE 1-3-10 Resist composition Evaluation Resist saving propertiesDefect inhibition performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 81 5 A A A A AA AA AA Example 82 5 A A A A AA AAAA Example 83 5 A A A A AA AA AA Example 84 5 A A A A AA AA AA Example85 5 A A A A AA AA AA Example 86 5 A A A A AA AA AA Example 87 5 A A A AAA AA AA Example 88 5 A A A A AA AA AA Example 89 5 A A A A AA AA AAExample 90 5 A A A A AA AA AA Example 91 5 A A A A AA AA AA Example 92 5A A A A AA AA AA Comparative 5 A A A C AA AA B Example 1 Comparative 5 AA A B AA AA B Example 2 Comparative 5 B A A A AA A AA Example 3Comparative 5 A A A B A AA A Example 4 Comparative 5 A A A C A AA AExample 5 Example 93 5 A A A B AA AA A Example 94 5 A A A B AA AA B

TABLE 1-3-11 Resist composition Evaluation Resist saving propertiesDefect inhibition performance Film Residue in Affinity thicknessunexposed Type Rsq1 SRsq Uniformity controllability Pattern collapseportion BRIDGE Example 81 6 A A A A AA AA AA Example 82 6 A A A A AA AAAA Example 83 6 A A A A AA AA AA Example 84 6 A A A A AA AA AA Example85 6 A A A A AA AA AA Example 86 6 A A A A AA AA AA Example 87 6 A A A AAA AA AA Example 88 6 A A A A AA AA AA Example 89 6 A A A A AA AA AAExample 90 6 A A A A AA AA AA Example 91 6 A A A A AA AA AA Example 92 6A A A A AA AA AA Comparative 6 A A A C AA AA B Example 1 Comparative 6 AA A B AA AA B Example 2 Comparative 6 B A A A AA A AA Example 3Comparative 6 A A A B A AA A Example 4 Comparative 6 A A A C A AA AExample 5 Example 93 6 A A A B AA AA A Example 94 6 A A A B AA AA B

Table 1 is divided into 33 tables of Table 1-1-1 to Table 1-3-11.

In Table 1, the chemical liquid of Example 1 is described in therespective lines of Table 1-1-1 to Table 1-1-11. That is, the chemicalliquid of the example is described in the first line in each of Table1-1-1 to Table 1-1-11. The tables show that the chemical liquid ofExample 1 contains a mixture of 95% by mass of DBCPN (the physicalproperties of DBCPN are as described in the tables) as a first organicsolvent and 5% by mass of GBL (the physical properties of GBL are asdescribed in the tables) as a third organic solvent without a secondorganic solvent, in which the content of an ether-based compound is 0mass ppm, and the mixture has physical properties including a vaporpressure of 381 Pa and a surface tension of 31.2 mN/m. Furthermore, thetables show that Rsq1 and SRsq indicating the affinity between thechemical liquid of Example 1 and the resist composition 1 are evaluatedas “A”, the chemical liquid of Example 1 is evaluated as “A” in terms ofuniformity, “A” in terms of film thickness controllability, “AA” interms of pattern collapse, “AA” in terms of residue in unexposedportion, and “AA” in terms of BRIDGE in a case where the chemical liquidis used for the resist composition 1. The tables show that Rsq1 and SRsqindicating the affinity between the chemical liquid of Example 1 and theresist composition 2 are evaluated as “A”, the chemical liquid ofExample 1 is evaluated as “A” in terms of uniformity, “A” in terms offilm thickness controllability, “AA” in terms of pattern collapse, “AA”in terms of residue in unexposed portion, and “AA” in terms of BRIDGE ina case where the chemical liquid is used for the resist composition 2.The tables show that Rsq1 and SRsq indicating the affinity between thechemical liquid of Example 1 and the resist composition 3 are evaluatedas “A”, the chemical liquid of Example 1 is evaluated as “A” in terms ofuniformity, “A” in terms of film thickness controllability, “AA” interms of pattern collapse, “AA” in terms of residue in unexposedportion, and “AA” in terms of BRIDGE in a case where the chemical liquidis used for the resist composition 3. The tables show that Rsq1 and SRsqindicating the affinity between the chemical liquid of Example 1 and theresist composition 4 are evaluated as “B” and “A” respectively, thechemical liquid of Example 1 is evaluated as “A” in terms of uniformity,“A” in terms of film thickness controllability, “AA” in terms of patterncollapse, “A” in terms of residue in unexposed portion, and “A” in termsof BRIDGE in a case where the chemical liquid is used for the resistcomposition 4. The tables show that Rsq1 and SRsq indicating theaffinity between the chemical liquid of Example 1 and the resistcomposition 5 are evaluated as “B” and “A”, the chemical liquid ofExample 1 is evaluated as “A” in terms of uniformity, “A” in terms offilm thickness controllability, “AA” in terms of pattern collapse, “A”in terms of residue in unexposed portion, and “A” in terms of BRIDGE ina case where the chemical liquid is used for the resist composition 5.The tables show that Rsq1 and SRsq indicating the affinity between thechemical liquid of Example 1 and the resist composition 6 are evaluatedas “B” and “A” respectively, the chemical liquid of Example 1 isevaluated as “A” in terms of uniformity, “A” in terms of film thicknesscontrollability, “AA” in terms of pattern collapse, “AA” in terms ofresidue in unexposed portion, and “A” in terms of BRIDGE in a case wherethe chemical liquid is used for the resist composition 6. The same shallbe applied to other examples and comparative examples. The componentsand the evaluation results of the chemical liquid of Example 41 aredescribed in Table 1-2-1 to Table 1-2-11. The components and theevaluation results of the chemical liquid of Example 81 are described inTable 1-3-1 to Table 1-3-11. The same shall be applied to other examplesand comparative examples.

In Table 1, “Content” of each organic solvent represents the content ofeach organic solvent in the mixture contained in the chemical liquid.

As described in Table 1, the chemical liquid of each of the examples hadthe effects of the present invention. In contrast, the chemical liquidof each of the comparative examples did not have the effects of thepresent invention.

The chemical liquid of Example 38, which contained a mixture having avapor pressure within a range of 160 to 1,000 Pa at 25° C., had resistsaving properties and defect inhibition performance better than those ofthe chemical liquid of Example 46. Furthermore, the chemical liquid ofExample 38 had defect inhibition performance better than that of thechemical liquid of Example 17.

What is claimed is:
 1. A chemical liquid comprising: a mixture of two ormore kinds of organic solvents; wherein the organic solvents areselected from the group consisting of compounds represented by Formulae(1) to (7), compounds represented by Formulae (9) to (11), a 3- to5-membered cyclic ketone compound that may have a substituent, a cyclicketone compound with 6 or more members that may have a substituent, alactone compound, and a lactam compound, the chemical liquid contains ordoes not contain an ether-based compound other than the compoundsrepresented by Formula (1), Formula (5), Formula (7), and Formulae (9)to (11), in a case where the chemical liquid contains the ether-basedcompound, a content of the ether-based compound in the chemical liquidis less than 10 mass ppm with respect to a total mass of the chemicalliquid, and the chemical liquid does not include a chemical liquid inwhich the mixture is formed of a lactone compound and the compoundrepresented by Formula (5), a chemical liquid in which the mixture isformed of the cyclic ketone compound with 6 or more members that mayhave a substituent and the compound represented by Formula (1), achemical liquid in which the mixture is formed of a lactone compound,the compound represented by Formula (1), and the compound represented byFormula (5), and a chemical liquid in which the mixture is formed of thecompound represented by Formula (1) and the compound represented byFormula (3),

in Formula (1), R₁₁ and R₁₂ each independently represent an alkyl group,R₁₃ represents a hydrogen atom or an alkyl group, and L₁ represents asingle bond or an alkylene group, in Formula (2), R₂₁ and R₂₂ eachindependently represent a hydrogen atom or an alkyl group, and L₂represents a single bond or an alkylene group, in Formula (3), R₃₁ andR₃₂ each independently represent a hydrogen atom or an alkyl group, atleast one of a plurality of R₃₂ 's represents an alkyl group, and L₃represents a single bond or an alkylene group, in Formula (4), R₄₁ andR₄₂ each independently represent an alkyl group, in Formula (5), R₅₁ andR₅₂ each independently represent an alkyl group, and L₅ represents asingle bond or an alkylene group, in Formula (6), R₆₁ and R₆₂ eachindependently represent an alkyl group, and R₆₁ and R₆₂ may form a ringby being bonded to each other, in Formula (7), R₇₁, Rn, R₇₃, and R₇₄each independently represent an alkyl group, and R₇₁ and R₇₂ may form aring by being bonded to each other, in Formula (9), R₉₁ and R₉₂ eachindependently represent an alkyl group, in Formula (10), L₁₀ representsa single bond or an alkylene group, and R₁₀₁ represents an alkyl group,and in Formula (11), L₁₁ represents a single bond or an alkylene group,and R₁₁₁ represents an alkyl group.
 2. A chemical liquid comprising: amixture of two or more kinds of organic solvents, wherein the mixturecontains γ-butyrolactone and at least one kind of organic solventselected from the group consisting of butyl acetate, ethyl lactate,2-hydroxymethyl isobutyrate, cyclopentanone dimethyl acetal,cyclopentanone, anisole, phenetole, ethylene glycol monomethyl etheracetate, 3-methoxymethyl propionate, and 3-ethoxyethyl propionate,contains dimethyl sulfoxide and at least one kind of organic solventselected from the group consisting of propylene glycol monomethyl etheracetate, butyl acetate, ethyl lactate, 2-hydroxymethyl isobutyrate,propylene glycol monomethyl ether, cyclopentanone dimethyl acetal,cyclopentanone, cyclohexanone, anisole, phenetole, ethylene glycolmonomethyl ether acetate, 3-methoxymethyl propionate, and 3-ethoxyethylpropionate, contains ethylene carbonate and at least one kind of organicsolvent selected from the group consisting of propylene glycolmonomethyl ether acetate, butyl acetate, ethyl lactate, 2-hydroxymethylisobutyrate, propylene glycol monomethyl ether, cyclopentanone dimethylacetal, cyclopentanone, cyclohexanone, anisole, phenetole, ethyleneglycol monomethyl ether acetate, 3-methoxymethyl propionate, and3-ethoxyethyl propionate, contains propylene carbonate and at least onekind of organic solvent selected from the group consisting of propyleneglycol monomethyl ether acetate, butyl acetate, ethyl lactate,2-hydroxymethyl isobutyrate, propylene glycol monomethyl ether,cyclopentanone dimethyl acetal, cyclopentanone, cyclohexanone, anisole,phenetole, ethylene glycol monomethyl ether acetate, 3-methoxymethylpropionate, and 3-ethoxyethyl propionate, contains1-methyl-2-pyrrolidone and at least one kind of organic solvent selectedfrom the group consisting of propylene glycol monomethyl ether acetate,butyl acetate, ethyl lactate, 2-hydroxymethyl isobutyrate, propyleneglycol monomethyl ether, cyclopentanone dimethyl acetal, cyclopentanone,cyclohexanone, anisole, phenetole, ethylene glycol monomethyl etheracetate, 3-methoxymethyl propionate, and 3-ethoxyethyl propionate,contains propylene glycol monomethyl ether acetate and at least one kindof organic solvent selected from the group consisting of butyl acetate,cyclopentanone dimethyl acetal, cyclopentanone, anisole, phenetole,ethylene glycol monomethyl ether acetate, 3-methoxymethyl propionate,and 3-ethoxyethyl propionate, contains cyclohexanone and at least onekind of organic solvent selected from the group consisting of butylacetate, ethyl lactate, 2-hydroxymethyl isobutyrate, propylene glycolmonomethyl ether, cyclopentanone dimethyl acetal, cyclopentanone,anisole, phenetole, ethylene glycol monomethyl ether acetate,3-methoxymethyl propionate, and 3-ethoxyethyl propionate, contains ethyllactate and at least one kind of organic solvent selected from the groupconsisting of butyl acetate, propylene glycol monomethyl ether,cyclopentanone dimethyl acetal, cyclopentanone, anisole, phenetole,ethylene glycol monomethyl ether acetate, 3-methoxymethyl propionate,and 3-ethoxyethyl propionate, contains 2-hydroxymethyl isobutyrate andat least one kind of organic solvent selected from the group consistingof butyl acetate, propylene glycol monomethyl ether, cyclopentanonedimethyl acetal, cyclopentanone, anisole, phenetole, ethylene glycolmonomethyl ether acetate, 3-methoxymethyl propionate, and 3-ethoxyethylpropionate, or contains cyclopentanone dimethyl acetal and at least onekind of organic solvent selected from the group consisting of butylacetate, propylene glycol monomethyl ether, cyclopentanone, anisole,phenetole, ethylene glycol monomethyl ether acetate, 3-methoxymethylpropionate, and 3-ethoxyethyl propionate.
 3. The chemical liquidaccording to claim 1, comprising: a mixture of two or more kinds of theorganic solvents.
 4. The chemical liquid according to claim 1, wherein avapor pressure of the mixture is 160 to 1,000 Pa at 25° C.
 5. Thechemical liquid according to claim 1, wherein the mixture contains afirst organic solvent which has a vapor pressure of 160 to 1,000 Pa at25° C. and a second organic solvent which has a vapor pressure higherthan 1,000 Pa at 25° C. or contains two or more kinds of the firstorganic solvents.
 6. The chemical liquid according to claim 1, whereinthe mixture contains a third organic solvent which has a vapor pressurelower than 160 Pa at 25° C.
 7. The chemical liquid according to claim 1,wherein a surface tension of the mixture is equal to or higher than 28mN/m at 25° C.
 8. The chemical liquid according to claim 1, wherein themixture contains an organic solvent having a Hansen solubility parameterhigher than 9.5 (MPa)^(0.5) in terms of a hydrogen bond element orhaving a Hansen solubility parameter higher than 15.5 (MPa)^(0.5) interms of a dispersion element.
 9. The chemical liquid according to claim1 that is used for pre-wetting.
 10. A pattern forming method comprising:a pre-wetting step of coating a substrate with the chemical liquidaccording to claim 1 so as to obtain a pre-wetted substrate; a resistfilm forming step of forming a resist film on the pre-wetted substrateby using an actinic ray-sensitive or radiation-sensitive resincomposition; an exposure step of exposing the resist film; and adevelopment step of developing the exposed resist film by using adeveloper, wherein the actinic ray-sensitive or radiation-sensitiveresin composition contains a resin including at least one kind ofrepeating unit selected from the group consisting of a repeating unitrepresented by Formula (a), a repeating unit represented by Formula (b),a repeating unit represented by Formula (c), a repeating unitrepresented by Formula (d), and a repeating unit represented by Formula(e),

R_(x1) to R_(x5) each independently represent a hydrogen atom or analkyl group which may have a substituent, R₁ to R₄ each independentlyrepresent a monovalent substituent, p1 to p4 each independentlyrepresent 0 or a positive integer, Ra represents a linear or branchedalkyl group, T₁ to T₅ each independently represent a single bond or adivalent linking group, R₅ represents a monovalent organic group, a to erepresent mol % and each independently represent a number included in arange of 0≤a≤100, 0≤b≤100, 0≤c<100, 0≤d<100, and 0≤e<100, provided thata+b+c+d+e=100 and a+b≠0, and the repeating unit represented by Formula(e) is different from all of the repeating units represented by Formula(a) to Formula (d).
 11. The pattern forming method according to claim10, wherein the chemical liquid with which the substrate is coated inthe pre-wetting step satisfies the following conditions 1 and 2 at 25°C., condition 1: Rsq1 calculated by Equation 1 based on a protonspin-spin relaxation time measured for the chemical liquid and a firsttest solution formed of the resin and the chemical liquid by using apulsed nuclear magnetic resonance-type particle interface characteristicevaluator is higher than 0.5,Rsq1=(τ0/τ1)−1  (Equation 1) in Equation 1, τ0 represents the spin-spinrelaxation time of the chemical liquid, and τ1 represents the spin-spinrelaxation time of the first test solution, condition 2: SRsq calculatedby Equation 2 based on the proton spin-spin relaxation time measured fora second test solution, which is formed of the resin and the chemicalliquid and in which the content of the resin is different from thecontent of the resin in the first test solution, and the first testsolution by using the pulsed nuclear magnetic resonance-type particleinterface characteristic evaluator is higher than −1,SRsq=(Rsq2−Rsq1)/(c2−c1)  (Equation 2) in Equation 2, Rsq1 represents avalue calculated by Equation 1, Rsq2 represents a value calculated bythe following Equation 3, c1 and c2 represent a mass-based content ofthe resin in the first test solution and the second test solutionrespectively, the unit of the mass-based content is % by mass, andc2>c1,Rsq2=(τ0/τ2)−1  (Equation 3) in Equation 3, τ0 has the same definitionas τ0 in Equation 1, and τ2 represents the spin-spin relaxation time ofthe second test solution.
 12. A kit comprising: the chemical liquidaccording to claim 1; and and an actinic ray-sensitive orradiation-sensitive resin composition which contains a resin includingat least one kind of repeating unit selected from the group consistingof a repeating unit represented by Formula (a), a repeating unitrepresented by Formula (b), a repeating unit represented by Formula (c),a repeating unit represented by Formula (d), and a repeating unitrepresented by Formula (e),

R_(x1) to R_(x5) each independently represent a hydrogen atom or analkyl group which may have a substituent, R₁ to R₄ each independentlyrepresent a monovalent substituent, p1 to p4 each independentlyrepresent 0 or a positive integer, Ra represents a linear or branchedalkyl group, T₁ to T₅ each independently represent a single bond or adivalent linking group, R₅ represents a monovalent organic group, a to erepresent mol % and each independently represent a number included in arange of 0≤a≤100, 0≤b≤100, 0≤c<100, 0≤d<100, and 0≤e<100, provided thata+b+c+d+e=100 and a+b≠0, and the repeating unit represented by Formula(e) is different from all of the repeating units represented by Formula(a) to Formula (d).
 13. A kit comprising: the chemical liquid accordingto claim 1; and an actinic ray-sensitive or radiation-sensitive resincomposition, wherein the actinic ray-sensitive or radiation-sensitiveresin composition contains a resin which has a repeating unit having aphenolic hydroxyl group and has a group generating a polar group bybeing decomposed by the action of an acid.
 14. A kit comprising: thechemical liquid according to claim 1; and an actinic ray-sensitive orradiation-sensitive resin composition, wherein the actinic ray-sensitiveor radiation-sensitive resin composition contains a hydrophobic resinand a resin which has a group generating a polar group by beingdecomposed by the action of an acid.
 15. A kit comprising: the chemicalliquid according to claim 1; and an actinic ray-sensitive orradiation-sensitive resin composition containing a resin, wherein thekit satisfies the following conditions 1 and 2, condition 1: Rsq1calculated by Equation 1 based on a proton spin-spin relaxation timemeasured at 25° C. for the chemical liquid and a first test solutionformed of the resin and the chemical liquid by using a pulsed nuclearmagnetic resonance-type particle interface characteristic evaluator ishigher than 0.5,Rsq1=(τ0/τ1)−1  (Equation 1) in Equation 1, τ0 represents the spin-spinrelaxation time of the chemical liquid, and τ1 represents the spin-spinrelaxation time of the first test solution, condition 2: SRsq calculatedby Equation 2 based on the proton spin-spin relaxation time measured at25° C. for a second test solution, which is formed of the resin and thechemical liquid and in which the content of the resin is different fromthe content of the resin in the first test solution, and the first testsolution by using the pulsed nuclear magnetic resonance-type particleinterface characteristic evaluator is higher than −1,SRsq=(Rsq2−Rsq1)/(c2−c1)  (Equation 2) in Equation 2, Rsq1 represents avalue calculated by Equation 1, Rsq2 represents a value calculated byEquation 3, c1 and c2 represent a mass-based content of the resin in thefirst test solution and the second test solution respectively, the unitof the mass-based content is % by mass, and c2>c1,Rsq2=(τ0/τ2)−1  (Equation 3) in Equation 3, τ0 has the same definitionas τ0 in Equation 1, and τ2 represents the spin-spin relaxation time ofthe second test solution.
 16. The chemical liquid according to claim 2,comprising: a mixture of two or more kinds of the organic solvents. 17.The chemical liquid according to claim 2, wherein a vapor pressure ofthe mixture is 160 to 1,000 Pa at 25° C.
 18. The chemical liquidaccording to claim 3, wherein a vapor pressure of the mixture is 160 to1,000 Pa at 25° C.
 19. The chemical liquid according to claim 2, whereinthe mixture contains a first organic solvent which has a vapor pressureof 160 to 1,000 Pa at 25° C. and a second organic solvent which has avapor pressure higher than 1,000 Pa at 25° C. or contains two or morekinds of the first organic solvents.
 20. The chemical liquid accordingto claim 3, wherein the mixture contains a first organic solvent whichhas a vapor pressure of 160 to 1,000 Pa at 25° C. and a second organicsolvent which has a vapor pressure higher than 1,000 Pa at 25° C. orcontains two or more kinds of the first organic solvents.